JPH0873408A - Production of beta-alkoxypropionic acid ester - Google Patents
Production of beta-alkoxypropionic acid esterInfo
- Publication number
- JPH0873408A JPH0873408A JP6208844A JP20884494A JPH0873408A JP H0873408 A JPH0873408 A JP H0873408A JP 6208844 A JP6208844 A JP 6208844A JP 20884494 A JP20884494 A JP 20884494A JP H0873408 A JPH0873408 A JP H0873408A
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- catalyst
- formula
- reaction
- alcohol
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 150000002148 esters Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 8
- 150000001340 alkali metals Chemical class 0.000 abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 8
- 150000004703 alkoxides Chemical class 0.000 abstract description 8
- 238000004821 distillation Methods 0.000 abstract description 7
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- -1 acrylate ester Chemical class 0.000 description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 4
- 238000011437 continuous method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000000075 primary alcohol group Chemical group 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 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
- 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β−アルコキシプロピオ
ン酸エステルの製造法に関し、さらに詳しくは、アクリ
ル酸エステルとアルコールとを反応させた後、触媒を含
有する反応終了液から効率よく生成物を回収するβ−ア
ルコキシプロピオン酸エステルの製造法に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a β-alkoxypropionic acid ester. More specifically, after reacting an acrylic acid ester with an alcohol, a product is efficiently produced from a reaction-terminated liquid containing a catalyst. The present invention relates to a method for producing a β-alkoxypropionic acid ester to be recovered.
【０００２】[0002]
【従来の技術】β−アルコキシプロピオン酸エステル
は、塗料用の溶剤、フォトレジスト現像液、洗浄用溶剤
等として工業的に重要な用途を有している。従来、β−
アルコキシプロピオン酸エステルの製造法としては、種
々の触媒によるアクリル酸エステルへのアルコールの付
加反応による方法が、収率も高く副生物も少ないことか
ら、優れた方法として知られている（Ｊ．Ｏｒｇ．Ｃｈ
ｅｍ．，４３（２１），４０８６，（１９７８）、欧州
特許１３６８５１号公報、特開昭６３−１０７９４９号
公報等）。触媒としては、通常塩基性物質が用いられ、
アルカリ金属あるいはアルカリ土類金属のアルコキシ
ド、水酸化物、および炭酸塩等が知られている。BACKGROUND OF THE INVENTION β-Alkoxypropionic acid esters have industrially important uses as solvents for paints, photoresist developers, cleaning solvents and the like. Conventionally, β-
As a method for producing an alkoxypropionic acid ester, a method involving addition reaction of alcohol to acrylic acid ester by various catalysts is known as an excellent method because of high yield and little by-products (J. Org). .Ch
em. , 43 (21), 4086, (1978), EP 136851, JP-A-63-107949, etc.). As the catalyst, a basic substance is usually used,
Alkoxides, hydroxides and carbonates of alkali metals or alkaline earth metals are known.
【０００３】上記触媒の中でも、アルカリ金属あるいは
アルカリ土類金属のアルコキシドを触媒とする方法は、
反応面では、収率的にも操作的にも有利であるが、反応
液に含有される触媒が、アクリル酸エステルに対して
０．１〜０．５モル％程度と非常に少ないにも関わら
ず、反応終了後、触媒の存在下、過剰のアルコールを留
去すると、白濁、さらにはゲル状物質が析出するという
問題点を有している。このゲル状物により最終的に撹拌
が非常に困難となり、このゲル状物質の除去には多大な
労力を必要とする。Among the above catalysts, the method using an alkoxide of an alkali metal or an alkaline earth metal as a catalyst is
In terms of reaction, it is advantageous in terms of yield and operation, but the amount of catalyst contained in the reaction solution is very small, about 0.1 to 0.5 mol% with respect to the acrylate ester. However, when the excess alcohol is distilled off in the presence of a catalyst after the completion of the reaction, there is a problem that white turbidity and further precipitation of a gel-like substance occur. Finally, the gel makes the stirring extremely difficult, and a great deal of labor is required to remove the gel.
【０００４】特開平３−２９１２５６号公報には、上記
の問題を解決する方法として、反応終了液中の過剰アル
コールを留去した後、中性塩の水溶液等で洗浄し、２層
分離させた後、製品を回収する方法が示されている。し
かし、水層中に塩が析出し、分液操作が煩雑になる場合
があり、また、製品の水層への溶解ロスや、有機層へ混
入した水分および洗浄に用いた有機溶媒と製品との分留
操作に伴うロスによって、製品の回収率が低下してしま
うという問題がある。As a method for solving the above-mentioned problems, Japanese Patent Application Laid-Open No. 3-291256 discloses that after distilling off excess alcohol in the reaction-terminated liquid, washing with an aqueous solution of a neutral salt or the like is carried out to separate two layers. Later, a method of collecting the product is shown. However, salt may be precipitated in the water layer, which may complicate the liquid separation operation.In addition, the dissolution loss of the product in the water layer, the water mixed in the organic layer and the organic solvent used for washing and the product There is a problem that the recovery rate of the product is reduced due to the loss accompanying the fractional distillation operation.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の問題
を解決し、アルカリ金属あるいはアルカリ土類金属のア
ルコキシドを触媒として用いて、得られた反応液から、
容易に、かつ効率よく製品の回収ができるβ−アルコキ
シプロピオン酸エステルの製造方法を提供するものであ
る。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and uses an alkali metal or alkaline earth metal alkoxide as a catalyst from a reaction solution obtained,
It is intended to provide a method for producing a β-alkoxypropionic acid ester which enables easy and efficient product recovery.
【０００６】[0006]
【課題を解決するための手段】本発明は下記一般式
（Ｉ）The present invention has the following general formula (I):
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】（式中、Ｒ1は炭素数１〜４の低級アルキ
ル基を示す）で表されるアルコールと、下記一般式(II)An alcohol represented by the formula (wherein R 1 represents a lower alkyl group having 1 to 4 carbon atoms) and the following general formula (II)
【０００９】[0009]
【化５】 [Chemical 5]
【００１０】（式中、Ｒ2はメチル基または水素原子で
あり、Ｒ3は炭素数１〜４の低級アルキル基を示す）で
表されるアクリル酸エステルとをアルカリ金属あるいは
アルカリ土類金属のアルコキシドを触媒として反応させ
て下記一般式(III)(Wherein R 2 represents a methyl group or a hydrogen atom, and R 3 represents a lower alkyl group having 1 to 4 carbon atoms) and an acrylic acid ester of an alkali metal or an alkaline earth metal. The following general formula (III)
【００１１】[0011]
【化６】 [Chemical 6]
【００１２】（式中、Ｒ1、Ｒ2、Ｒ3は上記と同じ）で
表されるβ−アルコキシプロピオン酸エステルを得、反
応が終了した溶液を強酸性陽イオン交換樹脂と接触させ
た後、蒸留精製することを特徴とするβ−アルコキシプ
ロピオン酸エステルの製造法を提供するものである。After obtaining the β-alkoxypropionic acid ester represented by the formula (wherein R 1 , R 2 and R 3 are the same as above) and contacting the reaction-completed solution with a strongly acidic cation exchange resin. The present invention provides a method for producing a β-alkoxypropionic acid ester, which is characterized in that it is purified by distillation.
【００１３】本発明に使用されるアルコールは１級また
は２級アルコールが好ましく、例えば、メタノール、エ
タノール、ｎ−プロパノール、イソプロパノール、ｎ−
ブタノール、イソブタノール等が挙げられる。The alcohol used in the present invention is preferably a primary or secondary alcohol, for example, methanol, ethanol, n-propanol, isopropanol, n-.
Examples thereof include butanol and isobutanol.
【００１４】本発明に使用される（メタ）アクリル酸エ
ステル（ここで（メタ）アクリル酸エステルとはアクリ
ル酸エステルおよびメタクリル酸エステルを総称して表
示するものである）は、例えば、（メタ）アクリル酸メ
チル、（メタ）アクリル酸エチル、（メタ）アクリル酸
ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メ
タ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブ
チル等が挙げられる。反応に使用されるアルコールは
（メタ）アクリル酸エステル１モルに対し、２〜２０モ
ルの過剰量用いられ、反応溶媒として使用することもで
きる。The (meth) acrylic acid ester used in the present invention (herein, (meth) acrylic acid ester is a generic term for acrylic acid ester and methacrylic acid ester) is, for example, (meth) Examples thereof include methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. The alcohol used in the reaction is used in an excess amount of 2 to 20 mol based on 1 mol of (meth) acrylic acid ester, and can also be used as a reaction solvent.
【００１５】使用される触媒の金属アルコキシドは、リ
チウム、ナトリウム、カリウム等のアルカリ金属、カル
シウム等のアルカリ土類金属のアルコキシドであり、炭
素数が１〜４の１級または２級アルコールのアルコキシ
ドが好ましく、例えば、ナトリウムメトキシド、ナトリ
ウムエトキシド、ナトリウムプロポキシド、ナトリウム
ブトキシド、カリウムメトキシド、カリウムエトキシド
等が挙げられる。また、反応に用いられるアルコールと
同一のアルコールのアルコキシドを用いることがさらに
好ましい。使用する触媒の量は、（メタ）アクリル酸エ
ステルに対し、０．１〜３．０モル％が好ましい。The metal alkoxide of the catalyst used is an alkoxide of an alkali metal such as lithium, sodium and potassium, an alkaline earth metal such as calcium, and an alkoxide of a primary or secondary alcohol having 1 to 4 carbon atoms. Preferred examples include sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, potassium ethoxide and the like. Further, it is more preferable to use an alkoxide of the same alcohol as the alcohol used in the reaction. The amount of the catalyst used is preferably 0.1 to 3.0 mol% based on the (meth) acrylic acid ester.
【００１６】反応は、通常、所定量の原料および触媒を
仕込み、回分式で行われるが、連続式で行うこともでき
る。反応温度は室温〜還流温度で、反応時間は１〜１０
時間の範囲である。反応終了後、反応液は必要に応じ、
室温程度まで冷却して強酸性陽イオン交換樹脂との接触
処理に供する。The reaction is usually carried out in a batch system by charging a predetermined amount of the raw material and the catalyst, but it can also be carried out in a continuous system. The reaction temperature is room temperature to reflux temperature, and the reaction time is 1 to 10
It is a range of time. After the reaction is completed, the reaction solution may be
It is cooled to about room temperature and subjected to contact treatment with a strongly acidic cation exchange resin.
【００１７】強酸性陽イオン交換樹脂と接触させるに際
し、反応液中の触媒濃度が高過ぎると、白濁、ゲル状物
質を生じるおそれがあるので、必要に応じ触媒の重量濃
度が０．２重量％以下になるように調製するのが好まし
い。この場合、反応に使用したアルコールで希釈して用
いることが好ましい。When contacting with the strongly acidic cation exchange resin, if the catalyst concentration in the reaction solution is too high, white turbidity or gel-like substance may be generated. Therefore, if necessary, the catalyst weight concentration is 0.2% by weight. It is preferable to prepare as follows. In this case, it is preferable to use it after diluting it with the alcohol used in the reaction.
【００１８】強酸性陽イオン交換樹脂は公知で一般に入
手できるものが使用可能であるが、好ましくはスルホン
酸基を有するものが使用される。交換容量は１．０ｍｅ
ｑ／ｍｌ以上、粒度範囲は１２００〜２００μのものが
好ましく、例えば三菱化成社製ＳＫシリーズ、ＰＫシリ
ーズ、ダウエックス社製５０Ｗ、ＭＳＣ−１，８８等が
挙げられる。これらのイオン交換樹脂は酸型で使用す
る。Ｎａ型の場合は塩酸等の酸で処理し、酸型として使
用する。As the strongly acidic cation exchange resin, those which are known and generally available can be used, but those having a sulfonic acid group are preferably used. Exchange capacity is 1.0me
It is preferably q / ml or more and has a particle size range of 1200 to 200 μ, and examples thereof include SK series and PK series manufactured by Mitsubishi Kasei Co., 50 W manufactured by Dowex Co., and MSC-1,88. These ion exchange resins are used in acid form. In the case of Na type, it is treated with an acid such as hydrochloric acid and used as an acid type.
【００１９】通常、これらのイオン交換樹脂は含水状態
で市販されているので、本発明の接触処理にそのまま用
いてもよいが、特に後述する連続式方法で処理する場合
には、処理に先立ち、反応に用いたアルコールと同一の
アルコールを樹脂の２〜５容量倍用いて溶媒置換して使
用するのが好ましい。使用量は、β−アルコキシプロピ
オン酸エステル生成反応に用いた触媒に対して１当量以
上、好ましくは１〜１０当量の交換容量を有すればよ
い。Since these ion exchange resins are usually commercially available in a water-containing state, they may be used as they are in the contact treatment of the present invention. However, particularly when they are treated by the continuous method described later, they are treated prior to the treatment. It is preferable to use the same alcohol as that used in the reaction by 2 to 5 times the volume of the resin and solvent substitution. The amount used may be 1 equivalent or more, preferably 1 to 10 equivalents, of the exchange capacity with respect to the catalyst used for the β-alkoxypropionic acid ester forming reaction.
【００２０】強酸性陽イオン交換樹脂と反応液の接触法
は、反応液中に樹脂を拡散させ、必要に応じ、攪拌、混
合し、０．５〜１０時間接触処理した後、樹脂を濾別す
る回分式方法、または樹脂を充填したカラムに反応液を
通液する連続式方法のいずれでもよい。接触処理の温度
は、室温〜使用するイオン交換樹脂の耐熱温度以下の範
囲である。連続式方法においては、反応液をＬＨＳＶ＝
１０Ｈｒ-1以下の流速で処理することが好ましい。ま
た、使用したイオン交換樹脂は酸処理等の方法により再
生して再使用可能である。The method of contacting the strongly acidic cation exchange resin with the reaction solution is as follows. The resin is diffused in the reaction solution, stirred and mixed if necessary, contact-treated for 0.5 to 10 hours, and then the resin is filtered off. Either a batch method or a continuous method in which the reaction solution is passed through a resin-filled column. The temperature of the contact treatment is in the range from room temperature to the heat resistant temperature of the ion exchange resin used. In the continuous method, the reaction solution is mixed with LHSV =
It is preferable to process at a flow rate of 10 Hr -1 or less. Further, the used ion exchange resin can be regenerated and reused by a method such as acid treatment.
【００２１】蒸留は接触処理後の反応液から常圧で過剰
アルコールを蒸留留去した後、徐々に減圧度を上げてい
き、β−アルコキシプロピオン酸エステルを室温〜１５
０℃の温度で分取できるよう減圧度を調整する（〜１０
ｍｍＨｇ）ことにより行われる。For the distillation, the excess alcohol is distilled off from the reaction solution after the contact treatment under atmospheric pressure, and then the degree of reduced pressure is gradually increased to remove the β-alkoxypropionic acid ester from room temperature to 15 ° C.
Adjust the degree of vacuum to allow fractionation at a temperature of 0 ° C (~ 10
mmHg).
【００２２】[0022]
【発明の効果】アルカリ金属あるいはアルカリ土類金属
のアルコキシド触媒を含有するβ−アルコキシプロピオ
ン酸エステル生成反応液は、強酸性陽イオン交換樹脂と
接触させることにより、蒸留中にゲル化することなく、
効率よくβ−アルコキシプロピオン酸エステルを回収す
ることができる。The β-alkoxypropionic acid ester-forming reaction liquid containing an alkali metal or alkaline earth metal alkoxide catalyst is brought into contact with a strongly acidic cation exchange resin without causing gelation during distillation.
The β-alkoxypropionic acid ester can be efficiently recovered.
【００２３】[0023]
【実施例】以下、本発明を実験例により詳細に説明す
る。 実施例１ 温度計、攪拌機および冷却器の付いた５００ｍｌの四つ
口フラスコ内にメタノール２０５．７ｇ（６．４ｍｏ
ｌ）を投入し、ナトリウムメトキシド０．２７ｇ（０．
００５ｍｏｌ）を溶解させた後、アクリル酸メチル８
６．１ｇ（１．０ｍｏｌ）を加えて、還流下（６４〜６
８℃）で約２時間反応させた。アクリル酸メチルの残存
率が１％以下であることを確認した後、反応液を室温程
度まで冷却した。The present invention will be described in detail below with reference to experimental examples. Example 1 205.7 g of methanol (6.4 mo) in a 500 ml four-necked flask equipped with a thermometer, a stirrer and a condenser.
1) and 0.27 g of sodium methoxide (0.
(005 mol) and then methyl acrylate 8
6.1 g (1.0 mol) was added and the mixture was refluxed (64-6).
The reaction was performed at 8 ° C for about 2 hours. After confirming that the residual ratio of methyl acrylate was 1% or less, the reaction solution was cooled to about room temperature.
【００２４】強酸性陽イオン交換樹脂 DIAION SK1BH
（三菱化成社製）２０ｍｌを直径２ｃｍのカラム管に充
填し、メタノール６０ｍｌを流して溶媒置換した。この
樹脂床に上述の反応液をＬＨＳＶ＝３Ｈｒ-1で通液し、
無色透明な溶液を得た。[0024] Strongly acidic cation exchange resin DIAION SK1BH
20 ml (manufactured by Mitsubishi Kasei Co., Ltd.) was filled in a column tube having a diameter of 2 cm, and 60 ml of methanol was flowed to replace the solvent. The above reaction solution was passed through this resin bed at LHSV = 3Hr −1 ,
A colorless transparent solution was obtained.
【００２５】得られた溶液を、減圧可能な水流ポンプを
備えた単蒸留装置に仕込んで、常圧にて過剰メタノール
を留去した後、徐々に減圧にして、６０〜６２℃／３３
ｍｍＨｇの留分として、ガスクロマトグラフィーで純度
９９．５％以上のβ−メトキシプロピオン酸メチル１０
５．５ｇ（８９３ｍｍｏｌ，収率８９％）を得た。蒸留
終了時まで、反応粗液中に白濁及びゲル状物は見られな
っかた。The obtained solution was placed in a simple distillation apparatus equipped with a water flow pump capable of reducing pressure, and after distilling off excess methanol at atmospheric pressure, the pressure was gradually reduced to 60 to 62 ° C./33.
As a fraction of mmHg, methyl β-methoxypropionate having a purity of 99.5% or more by gas chromatography 10
5.5 g (893 mmol, yield 89%) was obtained. No cloudiness or gel was observed in the reaction crude liquid until the end of distillation.
【００２６】比較例１ 上記実施例と同様に反応を行い、得られた反応溶液２８
０ｇを用い、常圧にて過剰メタノールを１６０ｇ留去し
た。この際、留去終了時には、反応液中にゲル状物質が
見られた。メタノール留去後、反応液１２０ｇを２５％
食塩水８０ｍｌで洗浄し、２層分離させた後、得られた
有機層を減圧下で蒸留を行い、６０〜６２℃／３３ｍｍ
Ｈｇの留分としてガスクロマトグラフィーで純度９９．
５％以上のβ−メトキシプロピオン酸メチル８９．３ｇ
（７５４ｍｍｏｌ，収率７５％）を得た。食塩水投入の
際、水層に食塩が析出するとともに一部のβ−メトキシ
プロピオン酸メチルが水層に溶解していることを確認し
た。また、蒸留の際、初留分として、β−メトキシプロ
ピオン酸メチルと水分の共沸組成物が見られた。Comparative Example 1 The reaction solution 28 obtained by carrying out the reaction in the same manner as in the above Example
Using 0 g, 160 g of excess methanol was distilled off under normal pressure. At this time, at the end of the distillation, a gel-like substance was found in the reaction solution. After distilling off methanol, 120 g of the reaction solution is 25%
After washing with 80 ml of saline and separating the two layers, the obtained organic layer was distilled under reduced pressure to obtain 60 to 62 ° C / 33 mm.
As a Hg fraction, a purity of 99.
89.3 g of methyl β-methoxypropionate of 5% or more
(754 mmol, yield 75%) was obtained. It was confirmed that when the salt solution was added, salt was precipitated in the aqueous layer and a part of methyl β-methoxypropionate was dissolved in the aqueous layer. Further, upon distillation, an azeotropic composition of methyl β-methoxypropionate and water was found as the first fraction.
───────────────────────────────────────────────────── 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)
で表されるアルコールと下記一般式(II) 【化２】 （式中、Ｒ2はメチル基または水素原子であり、Ｒ3は炭
素数１〜４の低級アルキル基を示す）で表される（メ
タ）アクリル酸エステルとを、アルカリ金属あるいはア
ルカリ土類金属のアルコキシドを触媒として反応させ下
記一般式(III) 【化３】 （式中、Ｒ1、Ｒ2、Ｒ3は上記と同じ）で表されるβ−
アルコキシプロピオン酸エステルを得、反応液を強酸性
陽イオン交換樹脂に接触させた後、蒸留することを特徴
とするβ−アルコキシプロピオン酸エステルの製造方
法。1. A compound represented by the following general formula (I) (In the formula, R 1 represents a lower alkyl group having 1 to 4 carbon atoms)
Alcohol represented by the following general formula (II): (In the formula, R 2 is a methyl group or a hydrogen atom, and R 3 is a lower alkyl group having 1 to 4 carbon atoms), and a (meth) acrylic acid ester represented by the formula: Of the following general formula (III): (Wherein R 1 , R 2 and R 3 are the same as above)
A method for producing β-alkoxypropionic acid ester, which comprises obtaining an alkoxypropionic acid ester, bringing the reaction solution into contact with a strongly acidic cation exchange resin, and then distilling it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6208844A JPH0873408A (en) | 1994-09-01 | 1994-09-01 | Production of beta-alkoxypropionic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6208844A JPH0873408A (en) | 1994-09-01 | 1994-09-01 | Production of beta-alkoxypropionic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0873408A true JPH0873408A (en) | 1996-03-19 |
Family
ID=16563042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6208844A Pending JPH0873408A (en) | 1994-09-01 | 1994-09-01 | Production of beta-alkoxypropionic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0873408A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008260699A (en) * | 2007-04-10 | 2008-10-30 | Hitachi Chem Co Ltd | METHOD FOR PRODUCING beta-ALKOXYPROPIONIC ACID ESTER |
-
1994
- 1994-09-01 JP JP6208844A patent/JPH0873408A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008260699A (en) * | 2007-04-10 | 2008-10-30 | Hitachi Chem Co Ltd | METHOD FOR PRODUCING beta-ALKOXYPROPIONIC ACID ESTER |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102811997A (en) | Sitagliptin intermediate compounds, preparation methods and uses thereof | |
| JP2002234859A (en) | Method for producing (meth)acrylic ester | |
| JP2002275132A (en) | Method for producing high-purity quaternary ammonium inorganic acid salt | |
| JPH0873408A (en) | Production of beta-alkoxypropionic acid ester | |
| JPS62265240A (en) | Method for reducing carboxylic acid | |
| US6162946A (en) | Processing for producing allyl 2-hydroxyisobutyrate | |
| JP3885497B2 (en) | Method for producing 1,2,4-butanetriol | |
| JPS6241662B2 (en) | ||
| JP2003261556A (en) | Method for producing (meth)acrylic acid ester | |
| JP4305388B2 (en) | Method for producing 1,2,4-butanetriol | |
| JP2002179622A (en) | Method for producing 4-acetoxystyrene | |
| JP5233154B2 (en) | Process for producing β-alkoxypropionic acid ester | |
| JP2903500B2 (en) | Method for producing 4-hydroxy-3,5,6-trifluorophthalic acid | |
| JPH09249657A (en) | Purification of glycidyl (meth)acrilate | |
| JP2001187763A (en) | Method for producing (meth)acrylic ester | |
| JPH07103071B2 (en) | Process for producing β-alkoxypropionate | |
| JPH0120152B2 (en) | ||
| JP3237541B2 (en) | Reduction method of aldehyde or ketone | |
| JP2002020332A (en) | Method for producing benzenedimethanol compound | |
| JP4314602B2 (en) | Process for producing optically active 3-hydroxypyrrolidine derivative | |
| JP2598488B2 (en) | Method for producing unsaturated carboxylic acid amide | |
| JPH03106847A (en) | Production of methacrylic acid ester | |
| JPH01283259A (en) | Production of carnitine | |
| JPH1129562A (en) | Production of 3-chloromethyl-3-alkyloxetane | |
| JPH0967297A (en) | Production of bistrifluoromethylbenzoic acids |