JPH07267900A - Production of high-purity 3-alkoxyisolactic acid esters - Google Patents
Production of high-purity 3-alkoxyisolactic acid estersInfo
- Publication number
- JPH07267900A JPH07267900A JP6083689A JP8368994A JPH07267900A JP H07267900 A JPH07267900 A JP H07267900A JP 6083689 A JP6083689 A JP 6083689A JP 8368994 A JP8368994 A JP 8368994A JP H07267900 A JPH07267900 A JP H07267900A
- Authority
- JP
- Japan
- Prior art keywords
- acid esters
- purity
- methacrylate
- catalyst
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
【０００１】[0001]
【産業上の利用分野】本発明は高純度３−アルコキシイ
ソ酪酸エステル類の製造法に関し、更に詳しくはメタク
リル酸エステル類とアルコ−ル類の反応による３−アル
コキシイソ酪酸エステル類の製造において、蒸留時の反
応液ｐＨを一定範囲に調整することを特徴とする高純度
３−アルコキシイソ酪酸エステル類の製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing high-purity 3-alkoxyisobutyric acid esters, more specifically, in the production of 3-alkoxyisobutyric acid esters by the reaction of methacrylic acid esters and alcohols. The present invention relates to a method for producing high-purity 3-alkoxyisobutyric acid esters, which comprises adjusting the pH of a reaction solution during distillation to a certain range.
【０００２】高純度３−アルコキシイソ酪酸エステル類
は香料、洗浄剤、溶剤、合成原料などの広い用途を有す
る有用な化合物である。High-purity 3-alkoxyisobutyric acid esters are useful compounds having a wide range of uses such as perfumes, detergents, solvents and synthetic raw materials.
【０００３】[0003]
【従来の技術】メタクリル酸エステル類とアルコ−ル類
から３−アルコキシイソ酪酸エステル類を製造する方法
は従来から種々知られている。例えば、ナトリウムメチ
ラ−ト触媒を用いて反応を行い、次いで硫酸あるいは酢
酸などで中和除去した後蒸留する方法（特開昭５４−９
２６３５号公報、Ｐ．Ｂｉｅｂｅｒ，Ａｎｎ．ｃｈｉ
ｍ．〔１２〕９ ６７４（１９５４））、触媒としてア
ミジン類を用いる方法（ＥＰ１３６８５１号公報）、触
媒として強塩基性イオン交換樹脂触媒を用いる方法（Ｅ
Ｐ２５４２９１号公報）などである。2. Description of the Related Art Various methods for producing 3-alkoxyisobutyric acid esters from methacrylic acid esters and alcohols have been conventionally known. For example, a method of carrying out a reaction using a sodium methylate catalyst, then neutralizing and removing with sulfuric acid or acetic acid and then distilling (JP-A-54-9).
2635, P.P. Bieber, Ann. chi
m. [12] 9 674 (1954)), a method using amidines as a catalyst (EP 136851), and a method using a strongly basic ion exchange resin catalyst as a catalyst (E
P254291).
【０００４】しかし、これらの従来方法で得られた３−
アルコキシイソ酪酸エステル類は電子材料用途、精密洗
浄用途、香料用途などの精密化学用途に使用する場合に
は酸性副生物などの不純物の混入が多く純度的に未だ不
十分であり、特に経済的効率を上げるために未反応原料
の回収再使用を行う場合に不純物の副生が顕著になると
いう問題点を有している。However, the 3-
Alkoxyisobutyric acid esters are not sufficiently pure in terms of purity due to the inclusion of impurities such as acidic by-products when they are used in precision chemical applications such as electronic material applications, precision cleaning applications, and perfume applications. When the unreacted raw material is recovered and reused in order to increase the yield, there is a problem that impurities by-products become remarkable.
【０００５】[0005]
【発明が解決しようとする課題】本発明は従来法におけ
る問題点を解決するためになされたもので、その目的は
工業的に有利に実施することのできる高純度３−アルコ
キシイソ酪酸エステル類の製造法を提供することにあ
り、具体的には製品中に混入する酸性副生物などの不純
物を低減させ電子材料用途、精密洗浄用途、香料用途な
どの精密化学分野に使用可能な高純度３−アルコキシイ
ソ酪酸エステル類の製造法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the problems in the conventional method, and the purpose thereof is to provide a high-purity 3-alkoxyisobutyric acid ester which can be industrially advantageously implemented. In order to provide a manufacturing method, specifically, it is possible to reduce impurities such as acidic by-products mixed in the product, and to use it in electronic chemical applications, precision cleaning applications, perfume applications and other high-precision chemical fields. It is to provide a method for producing alkoxyisobutyric acid esters.
【０００６】[0006]
【課題を解決するための手段】本発明者らは前記目的を
達成すべく種々検討を行った結果、メタクリル酸エステ
ル類とアルコ−ル類を塩基触媒下で反応させ蒸留して３
−アルコキシイソ酪酸エステル類を製造する際に、蒸留
前の反応液のｐＨを厳密に調整することにより、さらに
具体的には、蒸留前の反応液のｐＨを８から１０に調整
することにより、蒸留中の不純物の副生と混入を防止す
ることが可能となり、高純度の３−アルコキシイソ酪酸
エステル類が高收率で得られることを見いだし、本発明
を完成した。Means for Solving the Problems As a result of various studies to achieve the above object, the present inventors have found that methacrylic acid esters and alcohols are reacted under a base catalyst and distilled to obtain 3
-By strictly adjusting the pH of the reaction solution before distillation when producing the alkoxyisobutyric acid esters, more specifically, by adjusting the pH of the reaction solution before distillation to 8 to 10, The present invention has been completed by finding that it becomes possible to prevent impurities from being produced as a by-product and contamination during distillation, and that high-purity 3-alkoxyisobutyric acid esters can be obtained at a high yield.
【０００７】すなわち、本発明は、一般式（１） （式中Ｒ1 は炭素数８以下のアルキル基、シクロアルキ
ル基、またはアラルキル基を表す）で示されるメタクリ
ル酸エステル類と、一般式（２） Ｒ2 −ＯＨ （２） （式中Ｒ2 は炭素数４以下のアルキル基を表す）で示さ
れるアルコ−ル類を塩基触媒下で反応させた後に、反応
液を１０（wt％）含有する水溶液のｐＨが８から１０の
範囲となるように当該反応液のｐＨを調整し、しかる後
に蒸留することを特徴とする高純度３−アルコキシイソ
酪酸エステル類の製造法である。That is, the present invention is based on the general formula (1) (Wherein R 1 represents an alkyl group having 8 or less carbon atoms, a cycloalkyl group, or an aralkyl group), and a general formula (2) R 2 —OH (2) (wherein R 2 Represents an alkyl group having 4 or less carbon atoms), and after reacting the alcohols under a base catalyst, the pH of an aqueous solution containing 10 (wt%) of the reaction solution is adjusted to be in the range of 8 to 10. The method for producing high-purity 3-alkoxyisobutyric acid esters is characterized in that the pH of the reaction solution is adjusted and then distilled.
【０００８】以下、本発明を詳細に説明する。本発明の
方法は、メタクリル酸エステルとアルコ−ルを塩基触媒
下で反応させる反応工程および反応液のｐＨを調整後に
蒸留する蒸留工程よりなる。The present invention will be described in detail below. The method of the present invention comprises a reaction step of reacting a methacrylic acid ester and alcohol under a base catalyst and a distillation step of distilling after adjusting the pH of the reaction solution.
【０００９】本発明で用いるメタクリル酸エステル類
は、メタクリル酸メチル、メタクリル酸エチル、メタク
リル酸プロピル、メタクリル酸ブチル、メタクリル酸ヘ
キシル、メタクリル酸２−エチルヘキシル等のメタクリ
ル酸アルキル類、メタクリル酸シクロヘキシルなどのメ
タクリル酸シクロアルキル類、およびメタクリル酸ベン
ジル等のメタクリル酸アラルキル類などであり、好まし
くはメタクリル酸メチル、メタクリル酸エチル、メタク
リル酸ブチル、メタクリル酸シクロヘキシル、およびメ
タクリル酸ベンジル、更に好ましくはメタクリル酸メチ
ル、メタクリル酸エチルおよびメタクリル酸ブチルであ
る。Methacrylic acid esters used in the present invention include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate and 2-ethylhexyl methacrylate, and cyclohexyl methacrylate. Cycloalkyl methacrylates, and aralkyl methacrylates such as benzyl methacrylate, and the like, preferably methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate, more preferably methyl methacrylate, Ethyl methacrylate and butyl methacrylate.
【００１０】また、本発明に用いられるアルコ−ル類
は、メタノ−ル、エタノ−ル、プロパノ−ル、イソプロ
パノ−ル、ブタノ−ル、イソブタノ−ル、ｓｅｃ−ブタ
ノ−ル及びｔｅｒｔ−ブタノ−ルなどであり、好ましく
はメタノ−ル、エタノ−ル及びブタノ−ルである。アル
コ−ルの使用量はメタクリル酸エステル１モルに対しア
ルコ−ル０．５から１５モルの範囲、好ましくは１から
５モルの範囲である。The alcohols used in the present invention include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol and tert-butanol. And the like, preferably methanol, ethanol and butanol. The amount of alcohol used is in the range of 0.5 to 15 moles, preferably 1 to 5 moles, per mole of methacrylic acid ester.
【００１１】本発明に用いる塩基触媒としては、金属ナ
トリウムなどのアルカリ金属類、ナトリウムメチラ−
ト、カリウムｔ−ブトキシドなどのアルカリ金属アルコ
ラ−ト類、水酸化ナトリウム、水酸化カリウムなどのア
ルカリ金属水酸化物類、水酸化テトラメチルアンモニウ
ム、水酸化トリメチルベンジルアンモニウムなどの第四
級アンモニウム水酸化物類、および強塩基性イオン交換
樹脂類等が好ましい。触媒の使用量はメタクリル酸エス
テル１モルに対して０．０００１から１．０モル好まし
くは０．００５から０．２モルである。The base catalyst used in the present invention includes alkali metals such as sodium metal, sodium methyl
, Alkali metal alcoholates such as potassium t-butoxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and quaternary ammonium hydroxides such as tetramethylammonium hydroxide and trimethylbenzylammonium hydroxide. Materials and strongly basic ion exchange resins are preferred. The amount of the catalyst used is 0.0001 to 1.0 mol, preferably 0.005 to 0.2 mol, per 1 mol of methacrylic acid ester.
【００１２】反応温度は４０から１５０℃、好ましくは
６０から１２０℃である。反応は通常は常圧下で行われ
るが、減圧下あるいは加圧下で行っても何ら差し障りな
い。反応時間は反応温度、触媒量等により変化するが、
通常０．５から１８時間、好ましくは１から１０時間で
ある。The reaction temperature is 40 to 150 ° C, preferably 60 to 120 ° C. The reaction is usually carried out under normal pressure, but there is no problem even if it is carried out under reduced pressure or under increased pressure. The reaction time varies depending on the reaction temperature, the amount of catalyst, etc.,
It is usually 0.5 to 18 hours, preferably 1 to 10 hours.
【００１３】上記反応工程終了後に使用済みの触媒を分
離あるいは中和不活性化する。強塩基性イオン交換樹脂
のような固体触媒の場合は、濾過または遠心分離法によ
り分離する。均一系触媒の場合は、薄膜蒸発器等で直接
触媒と反応液を分離するか、酸で中和した後に、濾過、
遠心分離、もしくは、水洗等により抽出する方法により
分離するか、あるいは、触媒を分離せずに中和不活性
化、ｐＨ調整して、蒸留工程に供する等の処理をする。
均一系塩基触媒の場合、触媒の中和とｐＨ調整を同時に
行うこともできる。中和に使用する酸としては、硫酸、
塩酸、燐酸、硝酸、酢酸、プロピオン酸、ベンゼンスル
ホン酸、トルエンスルホン酸、酸性イオン交換樹脂など
が挙げられる。After the completion of the above reaction step, the used catalyst is separated or neutralized and deactivated. In the case of a solid catalyst such as a strongly basic ion exchange resin, it is separated by filtration or centrifugation. In the case of homogeneous catalysts, the catalyst and reaction liquid can be directly separated with a thin film evaporator or neutralized with an acid and then filtered,
It is separated by a method such as centrifugation or extraction by washing with water, or it is subjected to a treatment such as neutralization deactivation without adjusting the catalyst, adjusting the pH, and subjecting it to a distillation step.
In the case of a homogeneous base catalyst, neutralization of the catalyst and pH adjustment can be performed simultaneously. Acids used for neutralization include sulfuric acid,
Examples thereof include hydrochloric acid, phosphoric acid, nitric acid, acetic acid, propionic acid, benzenesulfonic acid, toluenesulfonic acid, acidic ion exchange resins and the like.
【００１４】本発明の方法では、反応液のｐＨを調整し
てから蒸留操作に移る。ｐＨの調整は、前記の触媒に用
いた塩基および触媒中和に用いた酸を使用して、８から
１０、好ましくは８．５から９．５の範囲となるように
調整する。しかし、反応液のｐＨを直接測定する方法で
は、反応液中の水分が少ないために測定値が一定せず、
正確に測定できない。本発明では、反応液の一部をサン
プリング、これを水で希釈して反応液を１０（wt％）含
有するｐＨ測定用の水溶液を調製し、この水溶液のｐＨ
を測定する方法とした。ｐＨが前記範囲内にない場合
は、反応液に酸または塩基を添加して再びｐＨを測定す
る。そして、ｐＨが前記の範囲内になるまでこの操作を
繰り返してｐＨを調整する。ｐＨ１０以上での蒸留は、
３−アルコキシイソ酪酸エステル類の分解に起因してメ
タクリル酸エステル類やアルコ−ル類の混入の多い製品
になり、ｐＨ８以下では、酸性副生物の混入が増大し、
共に純度不良で精密化学品用途には使用できなくなる。In the method of the present invention, the pH of the reaction solution is adjusted before the distillation operation. The pH is adjusted by using the base used for the catalyst and the acid used for the catalyst neutralization so as to be in the range of 8 to 10, preferably 8.5 to 9.5. However, in the method of directly measuring the pH of the reaction solution, the measured value is not constant because the water content in the reaction solution is small,
It cannot be measured accurately. In the present invention, a part of the reaction solution is sampled, diluted with water to prepare an aqueous solution for pH measurement containing 10 (wt%) of the reaction solution, and the pH of the aqueous solution is adjusted.
Was measured. If the pH is not within the above range, an acid or base is added to the reaction solution and the pH is measured again. Then, this operation is repeated until the pH falls within the above range to adjust the pH. Distillation at pH 10 or above
Due to the decomposition of 3-alkoxyisobutyric acid esters, the product becomes a product with a large amount of methacrylic acid esters and alcohols mixed, and at pH 8 or less, the mixing of acidic by-products increases,
Both cannot be used for precision chemicals due to poor purity.
【００１５】蒸留工程は、先ず常圧近辺で未反応アルコ
−ルの回収を行い、次いで常圧ないし減圧下で未反応メ
タクリル酸エステル類を回収し、最後に減圧下で製品の
３−アルコキシイソ酪酸エステル類を得る。メタクリル
酸エステルとアルコ−ルの反応は平衡反応であり、通常
は平衡反応率７０％以下で平衡組成に達してしまう。こ
のため、工業的には未反応回収原料のリサイクル使用が
不可欠になる。しかし、この回収原料の再使用を繰り返
すと、従来法では酸性副生物などがしだいに増加する難
点があった。ところが、本発明の蒸留前にｐＨ調整を行
う方法によれば、未反応原料の繰り返し使用による酸性
副生物などの増加は全く認められず、常に高純度の３−
アルコキシイソ酪酸エステル類を得ることが可能となっ
た。In the distillation step, first, unreacted alcohol is recovered in the vicinity of normal pressure, then unreacted methacrylic acid esters are recovered under normal pressure or reduced pressure, and finally, 3-alkoxyisolate of the product is reduced in reduced pressure. Butyric acid esters are obtained. The reaction between the methacrylic acid ester and the alcohol is an equilibrium reaction, and usually an equilibrium composition is reached at an equilibrium reaction rate of 70% or less. Therefore, industrially, it is indispensable to recycle the unreacted recovered raw material. However, when the reuse of the recovered raw material is repeated, the conventional method has a problem that the acid by-products and the like gradually increase. However, according to the method of adjusting the pH before distillation of the present invention, no increase in acidic by-products due to repeated use of the unreacted raw material is observed, and high purity 3-
It became possible to obtain alkoxyisobutyric acid esters.
【００１６】なお、本発明の反応工程、蒸留工程などの
各工程には、公知の重合禁止剤を添加することが好まし
く、重合禁止剤としては、例えば、ハイドロキノン、ハ
イドロキノンモノメチルエ−テル、ｔ−ブチルカテコ−
ル、フェノチアジン、クペロン等が適当である。A known polymerization inhibitor is preferably added to each step such as the reaction step and the distillation step of the present invention. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, t- Butyl catechol
Lu, phenothiazine, cuperone and the like are suitable.
【００１７】[0017]
【実施例】以下、実施例を示して本発明の方法を更に具
体的に説明するが、本発明は以下の実施例に何ら限定さ
れるものでない。EXAMPLES Hereinafter, the method of the present invention will be described more specifically by showing examples, but the present invention is not limited to the following examples.
【００１８】実施例１ 還流冷却器、温度計、および撹拌機を付した５００ｍｌ
反応器にメタクリル酸メチル１００ｇ（１モル）、メタ
ノール８０ｇ（２．５モル）、塩基性触媒としてナトリ
ウムメチラート３．１ｇ（０．０５７モル）、および重
合禁止剤としてハイドロキノン０．２４ｇを仕込み、浴
温９０℃のオイルバス中で２時間還流下に反応させた。
反応終了後、濃硫酸で塩基性触媒ナトリウムメチラート
を中和した。この時、中和は反応液の１０（wt％）水溶
液のｐＨが９．０になるように調節した。先ず常圧蒸留
でメタノールを留去した後、中和塩を濾別し、次いで１
２０mmHgでの減圧蒸留で未反応メタクリル酸メチルの回
収と目的物３−メトキシイソ酪酸メチルの取得を行っ
た。３−メトキシイソ酪酸メチル９２．２ｇ（収率６
９．８％、選択率９８．６％；共に仕込メタクリル酸メ
チル基準）が得られた。製品純度は９９．８％、酸性不
純物混入量は０．００２（wt％）であった。回収したメ
タノール、及びメタクリル酸メチルに消費した分を補充
して同様な反応精製操作を繰り返して行ったところ表１
の結果を得た。Example 1 500 ml equipped with reflux condenser, thermometer and stirrer
Charge 100 g (1 mol) of methyl methacrylate, 80 g (2.5 mol) of methanol, 3.1 g (0.057 mol) of sodium methylate as a basic catalyst, and 0.24 g of hydroquinone as a polymerization inhibitor into a reactor, The reaction was carried out under reflux in an oil bath with a bath temperature of 90 ° C. for 2 hours.
After the reaction was completed, the basic catalyst sodium methylate was neutralized with concentrated sulfuric acid. At this time, neutralization was adjusted so that the pH of a 10 (wt%) aqueous solution of the reaction solution was 9.0. After distilling off methanol by atmospheric distillation, the neutralized salt is filtered off, and then 1
Unreacted methyl methacrylate was recovered and the target product, methyl 3-methoxyisobutyrate, was obtained by vacuum distillation at 20 mmHg. Methyl 3-methoxyisobutyrate 92.2 g (yield 6
9.8%, selectivity 98.6%; both were based on charged methyl methacrylate). The product purity was 99.8%, and the amount of acidic impurities mixed was 0.002 (wt%). The recovered methanol and methyl methacrylate were replenished with the consumed amount, and the same reaction purification operation was repeated.
Got the result.
【００１９】[0019]
【表１】 [Table 1]
【００２０】比較例１ 触媒中和を塩基性触媒ナトリウムメチラートと当量の濃
硫酸で行った以外は全く同様に操作したところ表２の結
果を得た。なお、この操作での中和終了時の反応液の１
０（wt％）水溶液のｐＨは４．３から５．２の間であっ
た。Comparative Example 1 When the same procedure was conducted except that the catalyst neutralization was carried out with the basic catalyst sodium methylate and an equivalent amount of concentrated sulfuric acid, the results shown in Table 2 were obtained. In addition, 1 of the reaction liquid at the end of neutralization in this operation
The pH of the 0 (wt%) aqueous solution was between 4.3 and 5.2.
【００２１】[0021]
【表２】 [Table 2]
【００２２】実施例２ 触媒中和を酢酸で行い、この時反応液の１０（wt％）水
溶液のｐＨが５から１０．５の所定の値になるように調
節した以外は実施例１と全く同様に操作した。なお、塩
基触媒と当量の酢酸で中和した場合のｐＨは５．０であ
った。結果を表３にまとめた。Example 2 Catalytic neutralization was carried out with acetic acid, and except that the pH of a 10 (wt%) aqueous solution of the reaction solution was adjusted to a predetermined value of 5 to 10.5, the same as Example 1. The same operation was performed. The pH when neutralized with the same amount of acetic acid as the base catalyst was 5.0. The results are summarized in Table 3.
【００２３】[0023]
【表３】 [Table 3]
【００２４】実施例３ メタクリル酸メチルの代わりにメタクリル酸エチル１１
４ｇ（１モル）を、メタノールの代わりにエタノール２
３０ｇ（５モル）を、ナトリウムメチラートの代わりに
金属ナトリウム２．３ｇ（０．１モル）を用いた以外は
実施例１と同様の操作を繰り返したところ、３−エトキ
シイソ酪酸エチル９６．４ｇ（収率６０．２％、選択率
９８．２％；共に仕込メタクリル酸エチル基準）が得ら
れた。製品純度は９９．７％、酸性不純物混入量は０．
００２（wt％）であった。Example 3 Ethyl methacrylate 11 instead of methyl methacrylate
4 g (1 mol) of ethanol 2 instead of methanol
The same operation as in Example 1 was repeated except that 30 g (5 mol) of metal sodium was used instead of sodium methylate in an amount of 2.3 g (0.1 mol), and 96.4 g of ethyl 3-ethoxyisobutyrate ( The yield was 60.2%, the selectivity was 98.2%; both were based on the charged ethyl methacrylate. The product purity is 99.7%, and the amount of acidic impurities mixed is 0.
It was 002 (wt%).
【００２５】実施例４ メタクリル酸メチルの代わりにメタクリル酸ブチル１４
２ｇ（１モル）を、メタノールの代わりにブタノール２
９６ｇ（４モル）を、ナトリウムメチラートの代わりに
金属ナトリウム２．３ｇ（０．１モル）を用いた以外は
実施例１と同様の操作を繰り返したところ、３−ブトキ
シイソ酪酸ブチル９８．７ｇ（収率４５．７％、選択率
９８．６％；共に仕込メタクリル酸ブチル基準）が得ら
れた。製品純度は９９．８％、酸性不純物混入量は０．
００２（wt％）であった。EXAMPLE 4 Butyl methacrylate 14 instead of methyl methacrylate
2 g (1 mol) of butanol 2 instead of methanol
When the same operation as in Example 1 was repeated except that 96 g (4 mol) was replaced with sodium methylate and 2.3 g (0.1 mol) of sodium metal, 98.7 g of butyl 3-butoxyisobutyrate ( The yield was 45.7% and the selectivity was 98.6%; both were based on the charged butyl methacrylate. The product purity is 99.8%, and the amount of acidic impurities is 0.
It was 002 (wt%).
【００２６】実施例５ メタクリル酸メチルの代わりにメタクリル酸シクロヘキ
シル１６８ｇ（１モル）を用いた以外は実施例１と同様
の操作を繰り返したところ、３−メトキシイソ酪酸シク
ロヘキシル１３１．５ｇ（収率６５．７％、選択率９
６．６％；共に仕込メタクリル酸シクロヘキシル基準）
が得られた。製品純度は９９．８％、酸性不純物混入量
は０．００２（wt％）であった。Example 5 The same operation as in Example 1 was repeated except that 168 g (1 mol) of cyclohexyl methacrylate was used instead of methyl methacrylate, and 131.5 g of cyclohexyl 3-methoxyisobutyrate (yield 65. 7%, selectivity 9
6.6%; both are based on charged cyclohexyl methacrylate)
was gotten. The product purity was 99.8%, and the amount of acidic impurities mixed was 0.002 (wt%).
【００２７】[0027]
【発明の効果】従来法で得られた３−アルコキシイソ酪
酸エステル類は、酸性副生物などの不純物の混入が多
く、純度的に未だ不十分であった。特に、工業生産時の
経済的効率を上げるために未反応原料の回収再使用を行
う場合は、不純物の副生が顕著になるという問題点を有
しており、精密化学用途に使用するには純度的に未だ不
十分であった。しかし、本発明のメタクリル酸エステル
類とアルコ−ル類を塩基触媒下で反応させ、蒸留前に反
応液のｐＨを厳密に調整する方法により、蒸留中の不純
物の副生と混入を防止することが可能となり、高純度の
３−アルコキシイソ酪酸エステル類を高選択率で得るこ
とが可能となった。また、本発明の蒸留前にｐＨ調整を
行う方法によれば、未反応原料の繰り返し使用による酸
性副生物などの増加は全く認められず、リサイクル反応
によっても常に高純度の３−アルコキシイソ酪酸エステ
ルを得ることができる。本発明の方法によって、電子材
料用途、精密洗浄用途、香料用途などの精密化学分野に
使用可能な高純度３−アルコキシイソ酪酸エステル類の
製造が可能となった。EFFECTS OF THE INVENTION The 3-alkoxyisobutyric acid esters obtained by the conventional method are still inadequate in terms of purity due to a large amount of impurities such as acidic by-products mixed therein. In particular, when recovering and reusing unreacted raw materials in order to improve economic efficiency during industrial production, there is a problem that impurity by-products become remarkable, and it is not suitable for use in fine chemical applications. Purity was still insufficient. However, by the method of reacting the methacrylic acid esters and alcohols of the present invention under a base catalyst and strictly adjusting the pH of the reaction solution before distillation, it is possible to prevent by-products and contamination of impurities during distillation. It becomes possible to obtain high-purity 3-alkoxyisobutyric acid esters with high selectivity. In addition, according to the method of adjusting pH before distillation of the present invention, no increase in acidic by-products due to repeated use of unreacted raw materials is observed at all, and high purity 3-alkoxyisobutyric acid ester is always obtained even by recycling reaction. Can be obtained. According to the method of the present invention, it has become possible to produce high-purity 3-alkoxyisobutyric acid esters that can be used in the field of fine chemistry such as electronic material applications, precision cleaning applications, and perfume applications.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // C07B 61/00 300
Claims (1)
ル基、またはアラルキル基を表す）で示されるメタクリ
ル酸エステル類と、一般式（２） Ｒ2 −ＯＨ （２） （式中Ｒ2 は炭素数４以下のアルキル基を表す）で示さ
れるアルコ−ル類を塩基触媒下で反応させた後に、反応
液を１０（wt％）含有する水溶液のｐＨが８から１０の
範囲となるように当該反応液のｐＨを調整し、しかる後
に蒸留することを特徴とする高純度３−アルコキシイソ
酪酸エステル類の製造法。1. The general formula (1) (Wherein R 1 represents an alkyl group having 8 or less carbon atoms, a cycloalkyl group, or an aralkyl group), and a general formula (2) R 2 —OH (2) (wherein R 2 Represents an alkyl group having 4 or less carbon atoms), and after reacting the alcohols under a base catalyst, the pH of an aqueous solution containing 10 (wt%) of the reaction solution is adjusted to be in the range of 8 to 10. The method for producing high-purity 3-alkoxyisobutyric acid esters, which comprises adjusting the pH of the reaction solution, and then distilling the reaction solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6083689A JP2896846B2 (en) | 1994-03-31 | 1994-03-31 | Process for producing high-purity 3-alkoxyisobutyrate esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6083689A JP2896846B2 (en) | 1994-03-31 | 1994-03-31 | Process for producing high-purity 3-alkoxyisobutyrate esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07267900A true JPH07267900A (en) | 1995-10-17 |
| JP2896846B2 JP2896846B2 (en) | 1999-05-31 |
Family
ID=13809466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6083689A Expired - Lifetime JP2896846B2 (en) | 1994-03-31 | 1994-03-31 | Process for producing high-purity 3-alkoxyisobutyrate esters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2896846B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002000592A1 (en) * | 2000-06-27 | 2002-01-03 | Oleon N.V. | Production of alkoxycarboxylic esters as fatty acid alternatives |
| JP2014503474A (en) * | 2010-10-20 | 2014-02-13 | バイオフオーミツクス・インコーポレイテツド | Synthesis of methylene malonate using rapid recovery in the presence of energy transfer means |
-
1994
- 1994-03-31 JP JP6083689A patent/JP2896846B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002000592A1 (en) * | 2000-06-27 | 2002-01-03 | Oleon N.V. | Production of alkoxycarboxylic esters as fatty acid alternatives |
| JP2014503474A (en) * | 2010-10-20 | 2014-02-13 | バイオフオーミツクス・インコーポレイテツド | Synthesis of methylene malonate using rapid recovery in the presence of energy transfer means |
| JP2014508713A (en) * | 2010-10-20 | 2014-04-10 | バイオフオーミツクス・インコーポレイテツド | Synthesis of methylene malonate substantially free of impurities |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2896846B2 (en) | 1999-05-31 |
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