JP5608046B2 - Purification method of aldehyde - Google Patents
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Description
本発明は、アルデヒドの精製方法に関する。詳しくはアルデヒドを含む反応粗液を吸着剤で処理して、副反応促進物質を吸着除去することを特徴とするアルデヒドの精製方法に関する。 The present invention relates to a method for purifying aldehydes. More specifically, the present invention relates to a method for purifying aldehyde, which comprises treating a reaction crude liquid containing aldehyde with an adsorbent to adsorb and remove a side reaction promoting substance.
アルデヒド化合物は反応性に富んだ化合物であり、その反応性のために医薬、農薬等の中間体原料として重要な化合物である。しかしながらアルデヒド化合物はその反応性のため、蒸留精製中に副反応を起して高沸点副生成物となり収率の低下につながることが知られている（特許文献１）。特にα水素を有するアルデヒドでは酸性条件でも塩基性条件でもアルドール縮合が起きることが知られており（非特許文献１）、例えば、７−オクテン−１−アールでは、副生する７−オクテン酸によってアルドール縮合が促進されることが知られている（特許文献２）。 Aldehyde compounds are highly reactive compounds and are important compounds as intermediate raw materials for pharmaceuticals, agricultural chemicals and the like due to their reactivity. However, aldehyde compounds are known to cause side reactions during distillation purification and become high-boiling byproducts during distillation purification, leading to a decrease in yield (Patent Document 1). In particular, it is known that aldol condensation occurs in an aldehyde having α-hydrogen under acidic conditions or basic conditions (Non-patent Document 1). For example, in 7-octen-1-al, by-product 7-octenoic acid is used. It is known that aldol condensation is promoted (Patent Document 2).
アルデヒド以外の化合物については、蒸留精製中の副反応を、反応粗液中から原因物質を除去することで防ぐ方法がいくつか提案されている。グリシドールの精製の際に反応粗液を吸着剤にて処理して、粗液中の遷移金属の濃度を４００ｐｐｍ以下として、グリシドールの重合及びアルコールとの付加反応が進行することを防ぐ方法（特許文献３）、アルキルフェノール類の精製の際に無機固体塩基に接触させることで、酸性物質を除き、蒸留精製中に逆反応が進行することを防ぐ方法（特許文献４）、などが知られている。 For compounds other than aldehydes, several methods have been proposed for preventing side reactions during distillation purification by removing the causative substances from the reaction crude liquid. A method of preventing the progress of polymerization of glycidol and addition reaction with alcohol by treating the reaction crude liquid with an adsorbent during purification of glycidol so that the concentration of transition metal in the crude liquid is 400 ppm or less (Patent Document) 3) A method is known in which an acidic substance is removed by contact with an inorganic solid base during the purification of alkylphenols to prevent the reverse reaction from proceeding during distillation purification (Patent Document 4).
しかしながら、上記先行技術にはα水素を有するアルデヒドについて、アルドール縮合を抑えて効率よく蒸留精製を行った例はなく、現状ではα水素を有するアルデヒドを一般的な蒸留装置で蒸留精製することは困難である。よって、α水素を有するアルデヒドを、一般的な蒸留装置を用いて収率良く精製する方法の開発が望まれている。 However, in the above prior art, there is no example in which an aldehyde having α-hydrogen is efficiently purified by distillation while suppressing aldol condensation, and at present, it is difficult to purify aldehyde having α-hydrogen by distillation using a general distillation apparatus. It is. Therefore, development of a method for purifying aldehyde having α-hydrogen with high yield using a general distillation apparatus is desired.
本発明は、α水素を有するアルデヒドを蒸留精製するにあたり、加熱中における副反応（アルドール縮合）による高沸点化合物の生成を抑制し、回収率を低下させることなく精製する方法を提供することを課題とする。 It is an object of the present invention to provide a method for purifying an aldehyde having α-hydrogen by distillation without suppressing the production of high-boiling compounds due to side reactions (aldol condensation) during heating and reducing the recovery rate. And
本発明者らは上記問題を解決すべく鋭意検討した結果、アルデヒドを含む反応粗液を吸着剤で処理することで、反応粗液中の副反応促進物質が除去され、蒸留精製中のアルドール縮合を抑制できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have processed the reaction crude liquid containing aldehyde with an adsorbent, thereby removing side reaction promoting substances in the reaction crude liquid, and aldol condensation during distillation purification. Has been found to be able to be suppressed, and the present invention has been completed.
すなわち本発明は、以下に示すα水素を有するアルデヒドの精製方法に関する。
（１）α水素を有するアルデヒドを含む反応粗液を吸着剤で処理して副反応促進物質を吸着除去する工程を含むことを特徴とする、α水素を有するアルデヒドの精製方法。
（２）α水素を有するアルデヒドが７−オクテン−１−アールである、（１）記載の精製方法。
（３）吸着剤がＭｇ、ＡｌおよびＳｉから選ばれる１種類以上を主成分とする無機合成吸着剤である、（１）または（２）記載のアルデヒドの精製方法。
（４）吸着剤が下記式（Ｉ）で表される固体担体結合スカベンジャーである、（１）または（２）記載の精製方法。
That is, this invention relates to the purification method of the aldehyde which has the following alpha hydrogen.
(1) A method for purifying an aldehyde having an α hydrogen, comprising a step of treating a reaction crude liquid containing an aldehyde having an α hydrogen with an adsorbent to adsorb and remove a side reaction promoting substance.
(2) The purification method according to (1), wherein the aldehyde having α-hydrogen is 7-octen-1-al.
(3) The method for purifying an aldehyde according to (1) or (2), wherein the adsorbent is an inorganic synthetic adsorbent containing as a main component at least one selected from Mg, Al and Si.
(4) The purification method according to (1) or (2), wherein the adsorbent is a solid support-binding scavenger represented by the following formula (I).
α水素を有するアルデヒドを含む反応粗液からアルデヒドを蒸留で精製する際に、前記反応粗液を吸着剤と接触させることによって、副反応促進物質（アルドール縮合を促進してアルデヒド由来の高沸点副生物を副生させる要因となる物質）を吸着除去することで、アルドール縮合を抑え安定的にアルデヒドを蒸留精製することができる。 When purifying an aldehyde from a reaction crude liquid containing an aldehyde having α-hydrogen by distillation, the reaction crude liquid is brought into contact with an adsorbent, thereby promoting a side reaction promoting substance (accelerating aldol condensation to increase the high boiling By adsorbing and removing (substances that cause by-products of living organisms), aldehydes can be stably purified by distillation while suppressing aldol condensation.
（１）α水素を有するアルデヒド
本発明方法の対象となるα水素を有するアルデヒドは、以下の式（II）で示される。
(1) Aldehyde having α-hydrogen The aldehyde having α-hydrogen which is a target of the method of the present invention is represented by the following formula (II).
上記式（II）中、ＲはＣ1〜Ｃ15のアルキル基もしくはアルケニル基、またはアリル基、好ましくはＣ5〜Ｃ12のアルキル基もしくはアルケニル基、またはアリル基を表す。Ｒとしてより具体的には、ＣＨ2＝ＣＨ（ＣＨ2）4−基、Ｃ6Ｈ5−基等を表す。このようなアルデヒドの具体例としては、７−オクテン−１−アール、フェニルアセトアルデヒド等が挙げられる。これらのうちで最も好ましいものは７−オクテン−１−アールである。 In the above formula (II), R an alkyl or alkenyl group C 1 -C 15, or an allyl group, preferably an alkyl or alkenyl group or an allyl group, a C 5 -C 12. More specifically, R represents CH 2 ═CH (CH 2 ) 4 — group, C 6 H 5 — group or the like. Specific examples of such aldehydes include 7-octen-1-al and phenylacetaldehyde. Of these, the most preferred is 7-octen-1-al.
（２）反応粗液
本発明において、α水素を有するアルデヒドを含む反応粗液とは、α水素を有するアルデヒドの製造工程において得られるものであればいずれでもよく、その具体的製造方法は特に限定されないが、好ましくは出発物質として有機マグネシウム化合物を用い、Ｎ，Ｎ−ジメチルホルムアミドとグリニャール反応を行って得られる反応液である。
(2) Reaction crude liquid In the present invention, the reaction crude liquid containing an α-hydrogen-containing aldehyde may be any one obtained in the production process of an α-hydrogen-containing aldehyde, and its specific production method is particularly limited. However, it is preferably a reaction solution obtained by carrying out Grignard reaction with N, N-dimethylformamide using an organomagnesium compound as a starting material.
上記反応粗液には、一般的には３０〜７０重量％のα水素を有するアルデヒド、２５〜６５重量％の溶媒（テトラヒドロフラン（ＴＨＦ）、トルエンなど）などが含まれている。さらに副生成物として、酸性物質、アルコール等が含まれている。 The reaction crude liquid generally contains an aldehyde having 30 to 70% by weight of α-hydrogen, 25 to 65% by weight of a solvent (tetrahydrofuran (THF), toluene, etc.) and the like. Furthermore, acidic substances, alcohols and the like are included as by-products.
例えば、α水素を有するアルデヒドとして７−オクテン−１−アールを製造する工程において得られる前記反応粗液中には、一般的には３０〜７０重量％の７−オクテン−１−アールが含まれている。さらに副生成物として７−オクテン酸、７-オクテノール、その他構造不明の複数の副生成物、ジメチルアミンなどが含まれる。また、後処理に使用した無機物もわずかに残存する。 For example, the reaction crude liquid obtained in the step of producing 7-octen-1-al as an aldehyde having α-hydrogen generally contains 30 to 70% by weight of 7-octen-1-al. ing. Furthermore, 7-octenoic acid, 7-octenol, a plurality of other byproducts of unknown structure, dimethylamine, and the like are included as by-products. In addition, a slight amount of inorganic material used for the post-treatment remains.
本発明方法においてアルドール縮合を促進する原因物質（副反応促進物質）としては、必ずしも具体的に特定できるものではないが、アルデヒド製造工程で副生される物質（７−オクテン酸、ジメチルアミン、その他構造不明の副生成物）、残存する無機物(Ｍｇ塩など)が考えられる。α水素を有するアルデヒドを含む反応粗液においては、かかる副反応促進物質によって、蒸留精製中にアルデヒドが副反応（アルドール縮合反応）を起こして高沸点副生成物を生成し、このことが従来、収率の低下につながっていたが、本発明の方法によれば、副反応促進物質を吸着除去することによってかかる高沸点副生成物の生成が抑制される。 The causative substance (side reaction promoting substance) that promotes aldol condensation in the method of the present invention is not necessarily specified specifically, but is a substance (7-octenoic acid, dimethylamine, etc.) produced as a by-product in the aldehyde production process. By-products with unknown structure) and remaining inorganic substances (such as Mg salts) are conceivable. In a reaction crude liquid containing an aldehyde having α-hydrogen, the side reaction promoting substance causes a side reaction (aldol condensation reaction) during distillation purification to generate a high-boiling by-product. Although this has led to a decrease in yield, the method of the present invention suppresses the generation of such high-boiling by-products by adsorbing and removing the side reaction promoting substance.
（３）吸着剤
本発明においては、前記反応粗液を吸着剤で処理して副反応促進物質を吸着除去する。用いられる吸着剤としては、無機合成吸着剤類又は固体担体結合スカベンジャーが好ましい。
(3) Adsorbent In the present invention, the reaction crude liquid is treated with an adsorbent to adsorb and remove side reaction promoting substances. The adsorbent used is preferably an inorganic synthetic adsorbent or a solid support-bound scavenger.
無機合成吸着剤としては、Ｍｇ−Ａｌ−ＣＯ3系、ＭｇＯ−Ａｌ2Ｏ3系、及びＭｇＯ−
ＳｉＯ2系の無機合成吸着剤が挙げられる。このような無機合成吸着剤としては市販品を
用いることができ、例えば「キョーワード５００」（Mg6Al2(OH)16CO3・4H2O）、「キョ
ーワード６００」（2MgO・6SiO2・H2O）、「キョーワード７００」（Al2O3・9SiO2・H2O
）、「キョーワード１０００」（Mg4.5Al2(OH)13CO3・3.5H2O）、「ＫＷ−２０００」（Mg0.7Al0.3 O 1.15）、「ＤＨＴ−４Ａ」（いずれも商品名；協和化学工業（株）製）、「トミタ−ＡＤ５００ＮＳ」（Mg6Al2(OH)16CO3・4H2O）（商品名；富田製薬（株）製）など
がある。特に「キョーワード５００」、「トミタＡＤ５００ＮＳ」などが好ましい。
これらは微粉末タイプ、球状粒子の粉末タイプ（流動性がよい）、細粒状（非常に流動性がよい）、重質などがあるが、いずれも使用可能である。
Examples of the inorganic synthetic adsorbent include Mg—Al—CO 3 , MgO—Al 2 O 3 , and MgO—
Examples thereof include SiO 2 -based inorganic synthetic adsorbents. Commercially available products can be used as such inorganic synthetic adsorbents, such as “Kyoward 500” (Mg 6 Al 2 (OH) 16 CO 3 · 4H 2 O), “Kyoward 600” (2MgO · 6SiO 2).・ H 2 O), “KYOWARD 700” (Al 2 O 3 · 9SiO 2 · H 2 O
), “Kyoward 1000” (Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O), “KW-2000” (Mg 0.7 Al 0.3 O 1.15 ), “DHT-4A” (all trade names; Kyowa Chemical Industry Co., Ltd.), “Tomita-AD500NS” (Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O) (trade name; manufactured by Tomita Pharmaceutical Co., Ltd.), and the like. In particular, “KYOWARD 500”, “TOMITA AD500NS” and the like are preferable.
These include fine powder types, spherical particle powder types (good fluidity), fine particles (very good fluidity), heavy, etc., any of which can be used.
固体担体結合スカベンジャーはポリマーもしくはシリカの担体にスカベンジャー基を結合したものである。スカベンジャー基としては特に制限されないが、アミノ基、イミノ基
、メルカプト基などを有する有機基が挙げられる。具体的には、イミノジアセテート基、アミノメチルホスホン酸基、ベンゼンスルホン酸基、Ｎ，Ｎ−ジメチルアミノベンジル基、アミノプロピル基、メルカプトプロピル基等が挙げられる。
また、ポリマーとしては、ポリスチレンビーズ、ポリエチレングリコールビーズ等が挙げられる。
A solid support-bound scavenger is a scavenger group bound to a polymer or silica support. Although it does not restrict | limit especially as a scavenger group, The organic group which has an amino group, an imino group, a mercapto group etc. is mentioned. Specific examples include iminodiacetate group, aminomethylphosphonic acid group, benzenesulfonic acid group, N, N-dimethylaminobenzyl group, aminopropyl group, mercaptopropyl group and the like.
Examples of the polymer include polystyrene beads and polyethylene glycol beads .
このような固体担体結合スカベンジャーとしては市販品を用いることができ、例えばReaxa製のQuadraPureシリーズ（担体にポリスチレンビーズを使用）、及びQuadraSilシリーズ（担体に多孔性の球状シリカ樹脂を使用）がある。
QuadraPureシリーズとしては、QuadraPure IDA（-CH2-N(CH2COOH)2基）、QuadraPure SA
（-Ph-SO3H）、QuadraPure DMA（-Ph-CH2-N(CH3)2基）、QuadraPure AMPA（-CH2-NH-CH2-PO(OH)2基）などが挙げられる。QuadraSilシリーズとしては、QuadraSil AP（アミノプロピル基）、QuadraSil MP（メルカプトプロピル基）などが挙げられる。これらのうち、特にQuadra Pure SAが好ましい。
Commercially available products can be used as such a solid support-binding scavenger, such as QuadraPure series (using polystyrene beads for the support) and QuadraSil series (using porous spherical silica resin for the support) manufactured by Reaxa.
QuadraPure series includes QuadraPure IDA (-CH 2 -N (CH 2 COOH) 2 units), QuadraPure SA
(-Ph-SO 3 H), QuadraPure DMA (-Ph-CH 2 —N (CH 3 ) 2 groups), QuadraPure AMPA (—CH 2 —NH—CH 2 —PO (OH) 2 groups), etc. . QuadraSil series includes QuadraSil AP (aminopropyl group) and QuadraSil MP (mercaptopropyl group). Of these, Quadra Pure SA is particularly preferable.
（４）吸着剤除去工程
本発明においては、前記反応粗液を上記吸着剤で処理する。具体的には、反応粗液に吸着剤を添加して撹拌し、反応粗液中の副反応促進物質を吸着剤と接触させる。
(4) Adsorbent removal step In the present invention, the reaction crude liquid is treated with the adsorbent. Specifically, the adsorbent is added to the reaction crude liquid and stirred, and the side reaction promoting substance in the reaction crude liquid is brought into contact with the adsorbent.
吸着剤の使用量は、反応粗液中のα水素を有するアルデヒドの理論収量（反応が１００％進行したと仮定した場合に生じるアルデヒドの重量）に対して０．５〜４０重量％が好ましく、１.０〜２０重量％の範囲がより好ましく、２．０〜１０重量％の範囲が特に好ましい。また、反応粗液に対する吸着剤の使用量としては、α水素を有するアルデヒドを含む反応粗液全量に対し０．１５〜２８重量％が好ましく、より好ましくは０．３〜１４重量％である。
吸着剤の使用量が少なすぎると吸着の効果が低下する場合があり、多すぎると処理中にアルドール縮合が起こり純度低下する場合がある。
The amount of the adsorbent used is preferably 0.5 to 40% by weight with respect to the theoretical yield of aldehyde having α-hydrogen in the reaction crude liquid (weight of aldehyde generated when the reaction is assumed to proceed 100%), The range of 1.0 to 20% by weight is more preferable, and the range of 2.0 to 10% by weight is particularly preferable. The amount of the adsorbent used for the reaction crude liquid is preferably 0.15 to 28% by weight, more preferably 0.3 to 14% by weight, based on the total amount of the reaction crude liquid containing an aldehyde having α-hydrogen.
If the amount of the adsorbent used is too small, the effect of adsorption may be reduced, and if it is too large, aldol condensation may occur during the treatment and the purity may be reduced.
吸着剤添加後は、所定の温度範囲内で所定の処理時間、反応粗液を攪拌する。
吸着剤処理時間は、０．５〜１０時間の範囲が好ましく、より好ましくは１〜５時間である。処理時間が短すぎると吸着の効果が低下する場合があり、長すぎると処理中にアルドール縮合が起こり純度低下する場合がある。
After the adsorbent is added, the reaction crude liquid is stirred for a predetermined treatment time within a predetermined temperature range.
The adsorbent treatment time is preferably in the range of 0.5 to 10 hours, more preferably 1 to 5 hours. If the treatment time is too short, the effect of adsorption may be reduced, and if it is too long, aldol condensation may occur during the treatment and the purity may be lowered.
また、吸着剤処理は、０〜６０℃の温度範囲で行われるのが好ましく、より好ましくは０〜４０℃、特に好ましくは０〜３０℃である。吸着剤処理温度が４０℃を超えると処理中にアルドール縮合が起こり純度低下する場合がある。０℃未満では吸着の効果が低下する場合がある。 Moreover, it is preferable that an adsorption agent process is performed in the temperature range of 0-60 degreeC, More preferably, it is 0-40 degreeC, Most preferably, it is 0-30 degreeC. When the adsorbent treatment temperature exceeds 40 ° C., aldol condensation may occur during the treatment, resulting in a decrease in purity. If it is less than 0 degreeC, the effect of adsorption | suction may fall.
反応粗液は、所定時間攪拌した後、濾過することにより副反応促進物質を吸着した吸着剤を分離する。濾過方法は特に限定されないが、一般的な濾紙を用いる方法、一般的な濾布を用いた加圧濾過装置を用いる方法などが好ましい。 The reaction crude liquid is stirred for a predetermined time and then filtered to separate the adsorbent adsorbing the side reaction promoting substance. The filtration method is not particularly limited, but a method using a general filter paper, a method using a pressure filtration apparatus using a general filter cloth, and the like are preferable.
本発明においては、このような吸着剤処理によって反応粗液中の副反応促進物質が吸着除去されるものと思われるが、何が副反応促進物質であるかは必ずしも明らかではなく、このような吸着剤処理によって、蒸留精製後のアルデヒド回収率が格段に向上することは驚くべきことである。
In the present invention, it is considered that the side reaction promoting substance in the reaction crude liquid is adsorbed and removed by such an adsorbent treatment, but it is not necessarily clear what is the side reaction promoting substance. It is surprising that the aldehyde recovery after the distillation purification is remarkably improved by the adsorbent treatment.
以下に、実施例を挙げて本発明を説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
なお、下記実施例における各種測定値は、以下の方法によって求めた。
Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples.
Various measured values in the following examples were determined by the following methods.
（１）吸着処理の回収率
吸着処理の前後において、反応粗液についてガスクロマトグラフィー（島津製作所社製、商品名「ＧＣ-２０１４」；以下、「ＧＣ」と略す）による分析を行って７−オクテン−１−アールの濃度を求め、次の式により回収率を求めた。
［吸着処理の回収率（％）］＝［吸着処理後の７−オクテン−１−アールの溶媒分を除いた濃度］÷［吸着処理前の７−オクテン−１−アールの溶媒分を除いた濃度］×１００
(1) Recovery rate of adsorption treatment Before and after the adsorption treatment, the reaction crude liquid was analyzed by gas chromatography (manufactured by Shimadzu Corporation, trade name “GC-2014”; hereinafter abbreviated as “GC”). The concentration of octene-1-al was determined, and the recovery rate was determined by the following formula.
[Recovery rate of adsorption treatment (%)] = [concentration excluding 7-octen-1-al solvent after adsorption treatment] ÷ [excluding solvent content of 7-octen-1-al after adsorption treatment] Density] × 100
（２）加熱後の回収率
加熱処理（１００℃、２４時間）の前後において、反応粗液についてＧＣ分析を行って７−オクテン−１−アールの濃度を求め、次の式により回収率を求めた。
［加熱後の回収率（％）］＝［加熱後の７−オクテン−１−アールの溶媒分を除いた濃度］÷［吸着処理後（加熱前）の７−オクテン−１−アールの溶媒分を除いた濃度］×１００
(2) Recovery after heating Before and after heat treatment (100 ° C., 24 hours), the reaction crude liquid was subjected to GC analysis to determine the concentration of 7-octen-1-al, and the recovery rate was determined by the following equation. It was.
[Recovery rate after heating (%)] = [Concentration excluding solvent content of 7-octen-1-al after heating] ÷ [Solvent content of 7-octen-1-al after adsorption treatment (before heating) Concentration excluding]] × 100
[参考例1]
７−オクテン−１−アール［式（II）化合物のＲがＣＨ2＝ＣＨ（ＣＨ2）4−の場合］の製造：
還流冷却器、温度計、滴下ロートおよび攪拌機を備えた１Ｌ四頚フラスコを窒素置換し、これにマグネシウム２９．２ｇ（１．２モル）と少々のテトラヒドロフランと少々の臭化エチルを入れて撹拌しつつ還流するまで加熱し、マグネシウムを活性化した。次いで７−クロロ−１−ヘプテン１３２．６ｇ（１．０モル）をテトラヒドロフラン４８５ｍｌに溶解して４０℃で３時間かけて滴下ロートより滴下した。滴下後４０℃で３時間撹拌し、ヘプテニルマグネシウムクロライドを得た。
[Reference Example 1]
Production of 7-octen-1-al [when R of the compound of formula (II) is CH 2 ═CH (CH 2 ) 4 —]:
A 1 L four-necked flask equipped with a reflux condenser, thermometer, dropping funnel and stirrer was replaced with nitrogen, and 29.2 g (1.2 mol) of magnesium, a little tetrahydrofuran and a little ethyl bromide were added and stirred. While heating to reflux, magnesium was activated. Subsequently, 72.6 g (1.0 mol) of 7-chloro-1-heptene was dissolved in 485 ml of tetrahydrofuran and added dropwise from a dropping funnel at 40 ° C. over 3 hours. After dropping, the mixture was stirred at 40 ° C. for 3 hours to obtain heptenyl magnesium chloride.
このグリニャール試薬にトルエン１２７ｍｌで希釈したＮ，Ｎ−ジメチルホルムアミド１０９．６ｇ（１．５モル）を０〜１０℃で２時間かけて滴下し、更に同温度で３時間撹拌した。還流冷却器、温度計、滴下ロートおよび攪拌機を備えた２Ｌ四頚フラスコを窒素置換し、これに１０％硫酸１０００ｇを入れ、冷却撹拌しながら１０℃以下で反応粗液を滴下した。有機層を分離し、水洗、１０％炭酸ソーダ洗浄、水洗と行った。溶媒を留去して７−オクテン−１−アールを含む反応粗液（吸着処理前）１４１．６ｇを得た。この反応粗液中のＧＣ分析により求めた７−オクテン−１−アールの濃度は６４．０重量％（０．７２モル）であった。 To this Grignard reagent, 109.6 g (1.5 mol) of N, N-dimethylformamide diluted with 127 ml of toluene was added dropwise at 0 to 10 ° C. over 2 hours, and further stirred at the same temperature for 3 hours. A 2 L four-necked flask equipped with a reflux condenser, a thermometer, a dropping funnel and a stirrer was purged with nitrogen, and 1000 g of 10% sulfuric acid was added thereto, and the reaction crude liquid was added dropwise at 10 ° C. or lower with cooling and stirring. The organic layer was separated, washed with water, washed with 10% sodium carbonate, and washed with water. The solvent was distilled off to obtain 141.6 g of a crude reaction liquid (before adsorption treatment) containing 7-octen-1-al. The concentration of 7-octen-1-al determined by GC analysis in this reaction crude liquid was 64.0% by weight (0.72 mol).
[実施例1]
参考例１で得られた反応粗液（吸着処理前）１４１．６ｇに、７−オクテン−１−アールの理論収量（１２６．２ｇ）に対して５重量％の無機合成吸着剤（協和化学工業（株）製；キョーワード５００ＳＮ）６．３ｇを添加して２０℃で１時間攪拌した。次いで、副反応促進物質を吸着した無機合成吸着剤を濾紙（５Ｂ）にて濾過した後、１０ｇのトルエンで濾液の流路を２度洗浄し、７−オクテン−１−アールを含む反応粗液（吸着処理後）を得た。この反応粗液中のＧＣ分析により求めた７−オクテン−１−アールの含有量は８９．０ｇ（０．７０５モル）であった。
[Example 1]
141.6 g of the reaction crude liquid (before adsorption treatment) obtained in Reference Example 1 was 5% by weight of an inorganic synthetic adsorbent (Kyowa Chemical Industry) with respect to the theoretical yield (126.2 g) of 7-octen-1-al. 6.3 g (manufactured by Kyoward; Kyoward 500SN) was added and stirred at 20 ° C. for 1 hour. Next, after filtering the inorganic synthetic adsorbent adsorbing the side reaction promoting substance with a filter paper (5B), the flow path of the filtrate was washed twice with 10 g of toluene, and the reaction crude liquid containing 7-octen-1-al. (After adsorption treatment) was obtained. The content of 7-octen-1-al determined by GC analysis in this reaction crude liquid was 89.0 g (0.705 mol).
得られた７−オクテン−１−アールを含む反応粗液（吸着処理後）１５０．６ｇを、還流ヘッドとトップコンデンサーを備え、充填物として住友重機械工業株式会社製 住友／スルザーラボパッキング（２２ｍｍφ×５５ｍｍ）を２エレメント充填した蒸留塔を用いてバッチ蒸留を行い、沸点７１℃／２．７ｋＰａの留分７０．７ｇ（収量５６．０％）を得た。得られた留分のガスクロマトグラフィーによる分析純度は９９．２％であった。蒸留操作による７−オクテン−１−アールの回収率は９７．０％であった。 150.6 g of the obtained reaction crude liquid (after adsorption treatment) containing 7-octen-1-al was equipped with a reflux head and a top condenser, and as a filler, Sumitomo Heavy Industries, Ltd. Sumitomo / Sulzer Lab Packing (22 mmφ) Batch distillation was performed using a distillation column packed with 2 elements of × 55 mm) to obtain 70.7 g of a fraction having a boiling point of 71 ° C./2.7 kPa (yield: 56.0%). The analytical purity of the obtained fraction by gas chromatography was 99.2%. The recovery rate of 7-octen-1-al by distillation was 97.0%.
なお、蒸留操作による回収率は以下のとおり求めた。
蒸留前の反応粗液150.6ｇ中の７−オクテン−１−アール量；89.0g(0.705 mol)
蒸留の初留分中の７−オクテン−１−アール量；2.1g(0.017 mol)
蒸留の本留分中の７−オクテン−１−アール量；70.7g(0.560 mol)
蒸留の缶残分中の７−オクテン−１−アール量；12.0g(0.095 mol)
蒸留経路の付着分中の７−オクテン−１−アール量；1.5g(0.012 mol)
蒸留後の合計＝86.3g(0.684 mol)
蒸留操作による回収率＝86.3/89.0*100=97.0(%)
In addition, the recovery rate by distillation operation was calculated | required as follows.
7-octen-1-are the amount in the reaction crude liquid 150.6g before distillation; 89.0g (0.705 mol)
7-octen-1-are the amount in the initial distillate of the distillation; 2.1g (0.017 mol)
7-octen-1-I am content in the distillate of the distillation; 70.7g (0.560 mol)
7-octen-1-it is of cans residue in the distillation; 12.0g (0.095 mol)
7-octen-1-are amounts during deposition fraction of the distillation path; 1.5g (0.012 mol)
Total after distillation = 86.3g (0.684 mol)
Recovery by distillation operation = 86.3 / 89.0 * 100 = 97.0 (%)
また、上記７−オクテン−１−アールを含む反応粗液（吸着処理後）について、加熱による高沸点副生成物生成の影響をみるため、１００℃で２４時間加熱処理した。具体的には、該反応粗液（吸着処理後）を凍結アンプルに封管して１００℃に加熱して２４時間後に開封し、該加熱処理後の反応粗液中の７−オクテン−１−アール濃度をＧＣ分析で測定し、加熱後の回収率を求めた。その結果、７−オクテン−１−アールの加熱後の回収率は９４．６％であった。結果を表１に示す。
なお、蒸留操作中に起こるアルドール縮合は、副反応促進物質の存在下で加熱することにより進行すると考えられる。また、１００℃・２４時間という加熱処理条件は、多くの場合、実際の蒸留よりも過酷な条件となることから、上記加熱処理の前後で７−オクテン−１−アールの濃度を比較することによって、蒸留操作による影響をより明確に確認することができると考えられる。
In addition, the reaction crude liquid containing 7-octen-1-al (after the adsorption treatment) was subjected to heat treatment at 100 ° C. for 24 hours in order to examine the influence of high-boiling by-product formation due to heating. Specifically, the reaction crude liquid (after adsorption treatment) is sealed in a freezing ampoule, heated to 100 ° C. and opened after 24 hours, and 7-octene-1- in the reaction crude liquid after the heat treatment. The Earl concentration was measured by GC analysis, and the recovery after heating was determined. As a result, the recovery rate after heating of 7-octen-1-al was 94.6%. The results are shown in Table 1.
The aldol condensation that occurs during the distillation operation is considered to proceed by heating in the presence of a side reaction promoting substance. Moreover, since the heat treatment conditions of 100 ° C. and 24 hours are often severer conditions than actual distillation, by comparing the concentration of 7-octen-1-al before and after the heat treatment, It is considered that the influence of the distillation operation can be confirmed more clearly.
［実施例２〜１６］
実施例１に準じた方法で吸着剤の種類、添加量、攪拌温度、攪拌時間を変えて処理した。各反応粗液を１００℃、２４時間加熱した後の、７−オクテン−１−アールの回収率の結果を表１に示す。
[Examples 2 to 16]
By the method according to Example 1, the kind of adsorbent, the amount added, the stirring temperature, and the stirring time were changed. Table 1 shows the results of 7-octen-1-al recovery after heating each reaction crude liquid at 100 ° C. for 24 hours.
［比較例１］
実施例１に準じた方法で吸着剤での処理を省略した反応粗液を６０℃、５時間加熱した後の、７−オクテン−１−アールの回収率の結果を表１に示す。
[Comparative Example 1]
Table 1 shows the results of the recovery of 7-octen-1-al after heating the reaction crude liquid from which the treatment with the adsorbent was omitted at 60 ° C. for 5 hours by the method according to Example 1.
［比較例２〜５］
実施例１に準じた方法で吸着剤での処理を省略した反応粗液に添加剤を入れて６０℃、５時間加熱した後の、７−オクテン−１−アールの回収率の結果を表１に示す。
[Comparative Examples 2 to 5]
Table 1 shows the results of the recovery of 7-octen-1-al after adding the additive to the reaction crude liquid in which the treatment with the adsorbent was omitted by the method according to Example 1 and heating at 60 ° C. for 5 hours. Shown in
上記表１中の符号は以下の通りである。
※１）［吸着処理の回収率（％）］＝［吸着処理後の７−オクテン−１−アールの溶媒分を除いた濃度］÷［吸着処理前の７−オクテン−１−アールの溶媒分を除いた濃度］×100
※２）［加熱後の回収率（％）］＝［加熱後の７−オクテン−１−アールの溶媒分を除いた濃度］÷［吸着処理後の７−オクテン−１−アールの溶媒分を除いた濃度］×100
※３）加熱条件は６０℃で５時間。
The symbols in Table 1 are as follows.
* 1) [Recovery rate of adsorption process (%)] = [Concentration excluding 7-octen-1-al solvent after adsorption process] ÷ [Solvent content of 7-octen-1-al before adsorption process] Concentration excluding]] x 100
* 2) [Recovery rate after heating (%)] = [Concentration excluding solvent content of 7-octen-1-al after heating] ÷ [Solvent content of 7-octen-1-al after adsorption treatment] Excluded concentration] x 100
* 3) Heating conditions are 60 ° C for 5 hours.
また、上記表１中、使用した吸着剤は以下の通りである。
キョーワード５００ＳＮ（協和化学工業（株）；「ＳＮ」は細粒状のもの、以下同様）；Mg6Al2(OH)16CO3・4H2O、
キョーワード６００ＳＮ（協和化学工業（株））；2MgO・6SiO2 ・H 2 O
キョーワード７００ＳＮ（協和化学工業（株））；Al2O3・9SiO2 ・H 2O
キョーワード７００重質（協和化学工業（株））；Al2O3・9SiO2 ・H 2O
トミタ−ＡＤ５００ＮＳ（富田製薬（株））；Mg6Al2(OH)16CO3・4H2O
In Table 1, the adsorbents used are as follows.
KYOWARD 500SN (Kyowa Chemical Industry Co., Ltd .; "SN" is fine-grained, the same applies hereinafter); Mg 6 Al 2 (OH) 16 CO 3 · 4H 2 O,
KYOWARD 600SN (Kyowa Chemical Industry Co., Ltd.); 2MgO ・ 6SiO 2 ・ H 2 O
KYOWARD 700SN (Kyowa Chemical Industry Co., Ltd.); Al 2 O 3 · 9SiO 2 · H 2 O
KYOWARD 700 Heavy (Kyowa Chemical Industry Co., Ltd.); Al 2 O 3 · 9SiO 2 · H 2 O
Tomita-AD500NS (Tonda Pharmaceutical Co., Ltd.); Mg 6 Al 2 (OH) 16 CO 3 / 4H 2 O
QuadraPure IDA（Reaxa社製、スカベンジャー基；-CH2-N(CH2COOH)2基）
QuadraPure SA（Reaxa社製、スカベンジャー基；-Ph-SO3H基）、
QuadraPure DMA（Reaxa社製、スカベンジャー基；-Ph-CH2-N(CH3)2基）、
QuadraPure AMPA（Reaxa社製、スカベンジャー基；-CH2-NH-CH2-PO(OH)2基）
QuadraSil AP（Reaxa社製、スカベンジャー基；アミノプロピル基）、
QuadraSil MP （Reaxa社製、スカベンジャー基；メルカプトプロピル基）
QuadraPure IDA (Reaxa, scavenger group; -CH 2 -N (CH 2 COOH) 2 groups)
QuadraPure SA (Reaxa, scavenger group; -Ph-SO 3 H group),
QuadraPure DMA (Reaxa, scavenger group; -Ph-CH 2 -N (CH 3 ) 2 groups),
QuadraPure AMPA (Reaxa, scavenger group; —CH 2 —NH—CH 2 —PO (OH) 2 group)
QuadraSil AP (Reaxa, scavenger group; aminopropyl group),
QuadraSil MP (Reaxa, scavenger group; mercaptopropyl group)
表１の結果から分かるように、吸着剤処理を省略した比較例１の加熱処理後の回収率に比べて、本発明の吸着剤処理を行った場合（実施例１〜１６）の加熱処理後の回収率は格段に向上する。これによって、加熱の負荷がかかる蒸留操作においてもアルデヒドの回収率の低下が大幅に抑制され、安定的に収率良く回収できることが分かる。 As can be seen from the results in Table 1, after the heat treatment when the adsorbent treatment of the present invention was performed (Examples 1 to 16), compared with the recovery rate after the heat treatment of Comparative Example 1 in which the adsorbent treatment was omitted. The recovery rate is significantly improved. Thus, it can be seen that even in a distillation operation requiring a heating load, a decrease in the recovery rate of the aldehyde is greatly suppressed, and the recovery can be stably performed with a high yield.
また、酸性もしくは塩基性の不純物の混入が原因となって安定な蒸留を妨げる場合に、一般的な酸や塩基の添加で安定性を向上させられる場合があるが、そのような一般的な酸や塩基を添加した比較例２〜５の結果からすると顕著な効果は認められず、本発明の方法に比べて加熱後の回収率が格段に劣ることが分かる。 In addition, in the case where stable distillation is hindered due to mixing of acidic or basic impurities, the addition of a general acid or base may improve the stability. According to the results of Comparative Examples 2 to 5 to which a base was added, no remarkable effect was observed, and it was found that the recovery rate after heating was remarkably inferior compared with the method of the present invention.
なお、吸着剤は構造によってそれ自体が酸性あるいは塩基性を示す場合があるため、吸着剤処理中に該吸着剤に起因するアルドール縮合が起こり、純度低下（吸着処理前後における回収率の低下）が起こることが考えられるが、本発明では、吸着剤に起因する純度低下はあまり起こらないことが吸着処理の回収率の値から確認することができる。よって、本発明の吸着剤処理工程を含む精製方法は、高効率で優れた方法であることが分かる Since the adsorbent itself may be acidic or basic depending on the structure, aldol condensation due to the adsorbent occurs during the adsorbent treatment, resulting in a decrease in purity (reduction in recovery rate before and after the adsorption treatment). Although it may occur, in the present invention, it can be confirmed from the value of the recovery rate of the adsorption treatment that the purity decrease due to the adsorbent does not occur so much. Therefore, it can be seen that the purification method including the adsorbent treatment step of the present invention is a highly efficient and excellent method.
このように、本発明の方法によれば、α水素を有するアルデヒドの反応粗液精製工程において該反応粗液中の副反応促進物質を吸着除去する工程を含むことで、加熱中にアルドール縮合が起こることを抑えて、収率良くアルデヒドを蒸留精製できることがわかる。 As described above, according to the method of the present invention, the step of purifying the aldehyde having α-hydrogen includes the step of adsorbing and removing the side reaction promoting substance in the reaction crude liquid, thereby allowing aldol condensation to occur during heating. It can be seen that the aldehyde can be purified by distillation with good yield while suppressing the occurrence.
本発明によれば、α水素を有するアルデヒドを含む反応粗液から副反応促進物質を除去し、アルドール縮合を抑えることができるため、安定的に且つ収率よくα水素を有するアルデヒドを蒸留精製することができる。 According to the present invention, the side reaction promoting substance can be removed from the reaction crude liquid containing the aldehyde having α-hydrogen to suppress the aldol condensation, so that the aldehyde having α-hydrogen is distilled and purified stably and with a high yield. be able to.
Claims (3)
Ｍｇ 6 Ａｌ 2 （ＯＨ） 16 ＣＯ 3 ・４Ｈ 2 Ｏ、
２ＭｇＯ・６ＳｉＯ 2 ・Ｈ 2 Ｏ、
Ａｌ 2 Ｏ 3 ・９ＳｉＯ 2 ・Ｈ 2 Ｏ、
Ｍｇ 4.5 Ａｌ 2 （ＯＨ） 13 ＣＯ 3 ・３．５Ｈ 2 Ｏ、若しくは、
Ｍｇ 0.7 Ａｌ 0.3 Ｏ 1.15 のいずれかを主成分とする無機合成吸着剤、又は、
下記式（Ｉ）で表される固体担体結合スカベンジャーであって、
担体がポリマー、若しくはシリカ、
スカベンジャー基が−ＣＨ 2 −Ｎ（ＣＨ 2 ＣＯＯＨ） 2 基、−Ｐｈ−ＳＯ 3 Ｈ基、−Ｐｈ−ＣＨ 2 −Ｎ（ＣＨ 3 ） 2 基、−ＣＨ 2 −ＮＨ−ＣＨ 2 −ＰＯ（ＯＨ） 2 基、アミノプロピル基、及びメルカプトプロピル基から選ばれる、下記式（Ｉ）で表される固体担体結合スカベンジャーである吸着剤で処理する工程を含むことを特徴とする、７−オクテン−１−アールの精製方法。
Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O,
2MgO · 6SiO 2 · H 2 O,
Al 2 O 3 · 9SiO 2 · H 2 O,
Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O, or
Inorganic synthetic adsorbent mainly composed of any one of Mg 0.7 Al 0.3 O 1.15 , or
A solid support binding scavenger represented by the following formula (I):
The carrier is a polymer or silica,
The scavenger group is —CH 2 —N (CH 2 COOH) 2 group, —Ph—SO 3 H group, —Ph—CH 2 —N (CH 3 ) 2 group, —CH 2 —NH—CH 2 —PO (OH ) 2 group, aminopropyl group, and selected from mercaptopropyl group, characterized in that it comprises a step that processes an adsorption agent which is a solid support bound scavenger represented by the following formula (I), 7- octene - 1- are purification method.
である固体担体結合スカベンジャーである、請求項１記載の精製方法。 Adsorbent, the carrier is polystyrene beads, scavenger group -Ph-SO 3 H group
Solid carrier is bound scavenger claim 1 Symbol placement purification method is.
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| JPS56113725A (en) * | 1980-02-14 | 1981-09-07 | Mitsubishi Chem Ind Ltd | Separation of aliphatic aldehyde isomer mixture |
| JPS63185938A (en) * | 1987-01-28 | 1988-08-01 | Maruishi Seiyaku Kk | Purification of glutaraldehyde |
| JPS63196537A (en) * | 1987-02-10 | 1988-08-15 | Kansai Coke & Chem Co Ltd | Production of hydroformylated compound |
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| JP2001253843A (en) * | 2000-03-10 | 2001-09-18 | Daicel Chem Ind Ltd | Method for producing gamma, delta-unsaturated carbonyl compound |
| DE10014844B4 (en) * | 2000-03-24 | 2005-09-22 | Celanese Chemicals Europe Gmbh | Process for the recovery of rhodium from the hydroformylation products |
| US6995292B2 (en) * | 2002-09-16 | 2006-02-07 | Eastman Chemical Company | Process for reducing fluoride impurities resulting from use of fluorophosphite catalysts |
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