JP2001097893A - Method for producing high-purity organic compound - Google Patents
Method for producing high-purity organic compoundInfo
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- JP2001097893A JP2001097893A JP2000149636A JP2000149636A JP2001097893A JP 2001097893 A JP2001097893 A JP 2001097893A JP 2000149636 A JP2000149636 A JP 2000149636A JP 2000149636 A JP2000149636 A JP 2000149636A JP 2001097893 A JP2001097893 A JP 2001097893A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、不純物として昇華
性物質を含む粗有機化合物を効率よく蒸留精製すること
によって、高純度の有機化合物を製造する方法に関す
る。The present invention relates to a method for producing a high-purity organic compound by efficiently distilling and purifying a crude organic compound containing a sublimable substance as an impurity.
【０００２】[0002]
【従来の技術】従来、昇華性物質を不純物として含む高
沸点化合物を蒸留精製する場合、昇華性物質が昇華して
配管を閉塞する危険性があり、また、配管に付着した固
体の昇華性物質が後から留出してくる高沸点化合物に溶
解して、高沸点化合物の純度が上がらなくなるという問
題があり、蒸留精製は困難であった。2. Description of the Related Art Conventionally, when a high boiling point compound containing a sublimable substance as an impurity is purified by distillation, there is a risk that the sublimable substance sublimates and clogs a pipe, and a solid sublimable substance adhered to the pipe. However, there is a problem in that the compound is dissolved in a high-boiling compound distilled out later, and the purity of the high-boiling compound cannot be increased, so that purification by distillation has been difficult.
【０００３】一方、製品に対する純度の要求は年々高ま
ってきており、特に半導体製造プロセスに使用する製品
には金属成分の低減が厳しく要求されている。また、こ
のような金属成分を効率よく除去できる精製法として
は、蒸留精製が適している。[0003] On the other hand, the demand for purity of products has been increasing year by year, and in particular, products used in a semiconductor manufacturing process are strictly required to reduce metal components. Further, distillation purification is suitable as a purification method capable of efficiently removing such metal components.
【０００４】近年、アルキルアダマンチル（メタ）アク
リレートのポリマーは、半導体製造プロセスにおけるド
ライエッチング耐性が高いことが報告され（例えば特開
平５−２６５２１２号公報）、半導体用レジスト材料と
しての可能性が注目されている。これらアルキルアダマ
ンチル（メタ）アクリレートにおいても半導体用レジス
ト材料として使用する場合には金属成分が低減された高
純度のものが要求される。In recent years, it has been reported that a polymer of alkyl adamantyl (meth) acrylate has high dry etching resistance in a semiconductor manufacturing process (for example, Japanese Patent Application Laid-Open No. 5-265212), and its potential as a resist material for semiconductors has been attracting attention. ing. When these alkyl adamantyl (meth) acrylates are also used as resist materials for semiconductors, those having a reduced metal component and high purity are required.
【０００５】該アルキルアダマンチル（メタ）アクリレ
ートは、一般にアダマンタンを原料に、アダマンタノン
を経てアルキルアダマンタノールを得、これと（メタ）
アクリル酸、（メタ）アクリル酸エステル、（メタ）ア
クリル酸の無水物、又は（メタ）アクリル酸ハロゲン化
物との反応により製造できることが知られている。しか
し、目的化合物であるアルキルアダマンチル（メタ）ア
クリレートは高沸点の化合物であり、未反応原料や反応
副生成物として混入しているアダマンタン、アダマンタ
ノン、アルキルアダマンタノール等は、目的化合物の沸
点より昇華開始温度（昇華点）の低い昇華性物質である
ことから、目的化合物を蒸留により効率よく精製するこ
とが困難であった。[0005] The alkyl adamantyl (meth) acrylate is generally obtained from adamantane as a raw material, via adamantanone, to give an alkyladamantanol,
It is known that it can be produced by reacting with acrylic acid, (meth) acrylic acid ester, anhydride of (meth) acrylic acid or (meth) acrylic acid halide. However, the target compound, alkyladamantyl (meth) acrylate, is a compound having a high boiling point, and adamantane, adamantanone, alkyladamantanol, and the like mixed as unreacted raw materials and reaction by-products are sublimated from the boiling point of the target compound. Since it is a sublimable substance having a low onset temperature (sublimation point), it has been difficult to efficiently purify the target compound by distillation.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、以上のよう
に効率的な蒸留精製方法が知られていなかった、昇華性
物質を不純物として含む粗有機化合物について、効率的
な精製方法を採用して高純度の目的化合物を製造する方
法を提供することを目的とする。The present invention employs an efficient purification method for a crude organic compound containing a sublimable substance as an impurity, for which an efficient distillation purification method was not known as described above. To provide a method for producing a target compound of high purity by using the method.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記課題を
解決すべく鋭意検討を行った。その結果、目的とする有
機化合物の沸点より低い沸点を有する化合物の存在下に
粗有機化合物を蒸留することにより、目的とする有機化
合物を効率よく精製できることを見出し、本発明を完成
するに至った。Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, the present inventors have found that the desired organic compound can be efficiently purified by distilling the crude organic compound in the presence of a compound having a boiling point lower than the boiling point of the desired organic compound, and have completed the present invention. .
【０００８】即ち、本発明は、目的とする有機化合物の
沸点より低い温度で昇華する昇華性物質を不純物として
含む粗有機化合物を蒸留して高純度有機化合物を製造す
る方法において、該有機化合物の沸点より低い沸点を有
する化合物の存在下に該蒸溜を行ない、該有機化合物の
沸点より低い沸点を有する化合物の留出により、昇華し
て蒸留装置内部に付着した昇華性物質を洗い落とすか、
または、昇華性物質の蒸留装置内部への付着を防ぎ、次
いで留出する該有機化合物を回収することを特徴とする
高純度有機化合物の製造方法である。That is, the present invention provides a method for producing a high-purity organic compound by distilling a crude organic compound containing, as an impurity, a sublimable substance which sublimates at a temperature lower than the boiling point of the target organic compound. The distillation is performed in the presence of a compound having a boiling point lower than the boiling point, and a compound having a boiling point lower than the boiling point of the organic compound is distilled off to wash out a sublimable substance adhered to the inside of the distillation apparatus,
Alternatively, there is provided a method for producing a high-purity organic compound, which comprises preventing a sublimable substance from adhering to the inside of a distillation apparatus, and then collecting the organic compound distilled off.
【０００９】[0009]
【発明の実施の形態】本発明の方法では、目的とする有
機化合物の沸点より低い温度で昇華する昇華性物質（以
下、低温昇華性物質ともいう。）を含む粗有機化合物
（以下、被精製物ともいう。）を蒸留する。このとき被
精製物としては、低温昇華性物質を含む粗有機化合物で
あれば特に限定されない。例えば、（ｉ）目的とする有
機化合物の沸点より低い温度で昇華する昇華性物質を原
料として化学反応により該有機化合物を合成して得られ
る、未反応原料が残存する反応液、（ii）或いは該反応
液から得られる粗生成物であって前記原料を不純物とし
て含むもの、又は（iii）化学反応により有機化合物を
合成する際に副生成物として生成し、該有機化合物の沸
点より低い温度で昇華する昇華性物質を含む反応液、或
いは（iv）該反応液から得られる粗生成物であって前記
副生成物を不純物として含むものなどが使用される。BEST MODE FOR CARRYING OUT THE INVENTION In the method of the present invention, a crude organic compound containing a sublimable substance (hereinafter, also referred to as a low-temperature sublimable substance) that sublimes at a temperature lower than the boiling point of the target organic compound (hereinafter referred to as a purified substance) Is also distilled. At this time, the object to be purified is not particularly limited as long as it is a crude organic compound containing a low-temperature sublimable substance. For example, (ii) a reaction solution obtained by synthesizing an organic compound by a chemical reaction using a sublimable substance that sublimes at a temperature lower than the boiling point of the target organic compound and remaining unreacted raw materials, (ii) or A crude product obtained from the reaction solution containing the raw material as an impurity, or (iii) produced as a by-product when synthesizing an organic compound by a chemical reaction, at a temperature lower than the boiling point of the organic compound. A reaction solution containing a sublimable substance to be sublimated, or (iv) a crude product obtained from the reaction solution and containing the by-product as an impurity is used.
【００１０】上記のように有機化合物の合成反応におい
て昇華性の合成原料や反応副生物が不可避的に混入する
ような有機化合物としては、アルキルアダマンチルエス
テルを挙げることができる。アルキルアダマンチルエス
テルの合成反応においては、昇華性物質であるアダマン
タン、アダマンタノン、アルキルアダマンタノール等の
合成原料や合成反応における副生成物が生成物中に不可
避的に混入する。このような合成反応において得られる
粗有機化合物は、本発明における蒸溜の対象物として好
適である。As described above, examples of the organic compound in which a sublimable synthetic raw material or a reaction by-product is inevitably mixed in the organic compound synthesis reaction include alkyl adamantyl esters. In the synthesis reaction of an alkyl adamantyl ester, synthesis raw materials such as adamantane, adamantanone, and alkyl adamantanol, which are sublimable substances, and by-products in the synthesis reaction are unavoidably mixed into the product. The crude organic compound obtained in such a synthesis reaction is suitable as an object of distillation in the present invention.
【００１１】上記のアルキルアダマンチルエステルは、
常圧における沸点が１００℃以上、１ｍｍＨｇの減圧下
で４０℃以上であるような高沸点の化合物であり、この
ような有機化合物の沸点と低温昇華性物質の昇華開始温
度との差が１０℃以上、特に２０〜１００℃である場合
に、本発明の方法は特に好適である。The above alkyl adamantyl ester is
A compound having a high boiling point such that the boiling point at normal pressure is 100 ° C. or higher and 40 ° C. or higher under a reduced pressure of 1 mmHg, and the difference between the boiling point of such an organic compound and the sublimation start temperature of the low-temperature sublimable substance is 10 ° C. As described above, the method of the present invention is particularly preferable when the temperature is 20 to 100 ° C.
【００１２】例えば、アダマンタンを原料に、アダマン
タノンを経てアルキルアダマンタノールを得、これと
（メタ）アクリル酸、（メタ）アクリル酸エステル、
（メタ）アクリル酸の無水物、又は（メタ）アクリル酸
ハロゲン化物等との反応によりアルキルアダマンチル
（メタ）アクリレート等のアルキルアダマンチルエステ
ルが製造される。この場合、得られる反応液あるいは該
反応液から得られる粗製品は、一般に、未反応原料や反
応副生成物であるアダマンタン、アダマンタノン、アル
キルアダマンタノール等を不純物として含んでおり、こ
れらの不純物は蒸留時の真空度にもよるが、一般に目的
化合物であるアルキルアダマンチルエステルの沸点より
昇華開始温度が１００℃〜１０℃程度低い低温昇華性物
質である。この様な反応液等から目的化合物を蒸溜によ
り精製する方法として本発明の方法を特に好適に採用す
ることができる。For example, using adamantane as a raw material, an alkyl adamantanol is obtained via adamantanone, and this is combined with (meth) acrylic acid, (meth) acrylate,
An alkyl adamantyl ester such as an alkyl adamantyl (meth) acrylate is produced by a reaction with an anhydride of (meth) acrylic acid or a halide of (meth) acrylic acid. In this case, the obtained reaction solution or a crude product obtained from the reaction solution generally contains unreacted raw materials and reaction by-products such as adamantane, adamantone, and alkyladamantanol as impurities. Although it depends on the degree of vacuum at the time of distillation, it is a low-temperature sublimable substance whose sublimation start temperature is generally lower by about 100 ° C. to 10 ° C. than the boiling point of the alkyl adamantyl ester as the target compound. The method of the present invention can be particularly preferably employed as a method for purifying the target compound from such a reaction solution by distillation.
【００１３】上記の方法で製造されるアルキルアダマン
チルエステルは、下記一般式（１）The alkyl adamantyl ester produced by the above method has the following general formula (1)
【００１４】[0014]
【化１】 Embedded image
【００１５】（式中、Ｒ3は水素原子又は炭素数１〜６
のアルキル基であり、Ｒ4は水素原子又はメチル基であ
る。）で示される。(Wherein R 3 is a hydrogen atom or a carbon number of 1 to 6)
And R 4 is a hydrogen atom or a methyl group. ).
【００１６】前記一般式（２）において、Ｒ3は炭素数
１〜６のアルキル基であり、Ｒ4は水素原子又はメチル
基である。Ｒ3で示されるアルキル基を具体的に例示す
れば、メチル基、エチル基、プロピル基、ブチル基、ヘ
キシル基等の直鎖アルキル基；及びイソプロピル基、第
３級ブチル基、ネオペンチル基等の分岐アルキル基を挙
げることができる。特に、半導体用レジストの原料とし
て有用であり、特に高純度化が重要であるという観点か
ら、前記一般式（２）で示されるもの中でもＲ3がメチ
ル基、エチル基、またはブチル基であり、Ｒ4が水素ま
たはメチル基であるものが好適である。In the general formula (2), R 3 is an alkyl group having 1 to 6 carbon atoms, and R 4 is a hydrogen atom or a methyl group. Specific examples of the alkyl group represented by R 3 include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group and hexyl group; and isopropyl group, tertiary butyl group, neopentyl group and the like. Examples include branched alkyl groups. In particular, R 3 is a methyl group, an ethyl group, or a butyl group among those represented by the general formula (2) from the viewpoint that it is useful as a raw material of a resist for a semiconductor, and that high purification is particularly important. Those in which R 4 is hydrogen or a methyl group are preferred.
【００１７】本発明においては、被精製物には、目的と
する有機化合物及び低温華性物質以外の物質（以下、第
三物質ともいう。）、例えば、昇華性を有さない物質、
或いは昇華性を有していても昇華開始温度が目的とする
有機化合物の沸点よりも高い物質を含んでいてもよい。
通常、第三物質となり得る化合物としては、目的とする
有機化合物の合成時に用いる原料、副生成物、溶媒など
が挙げられる。In the present invention, the substance to be purified includes a substance other than the target organic compound and the low-temperature sublimable substance (hereinafter, also referred to as a third substance), for example, a substance having no sublimability,
Alternatively, a substance having a sublimation property but having a sublimation start temperature higher than the boiling point of the target organic compound may be contained.
Usually, as the compound that can be the third substance, a raw material, a by-product, a solvent, and the like used in synthesizing a target organic compound can be given.
【００１８】また、被精製物の組成は特に限定されない
が、蒸留効率などの点から目的とする有機化合物と低温
昇華性物質との総重量を基準として、目的とする有機化
合物が５０〜９９重量％、特に７０〜９９重量％である
のが好適である。また、第三物質を含む場合には、該第
三物質の含有量は前記総重量を１００重量部としたとき
に５０重量部以下、特に３０重量部以下であるのが好適
である。The composition of the object to be purified is not particularly limited, but the amount of the target organic compound is 50 to 99% by weight based on the total weight of the target organic compound and the low-temperature sublimable substance in terms of distillation efficiency and the like. %, Especially 70-99% by weight. When a third substance is contained, the content of the third substance is preferably not more than 50 parts by weight, particularly preferably not more than 30 parts by weight when the total weight is 100 parts by weight.
【００１９】本発明においては、前記被精製物の蒸留
を、目的とする有機化合物の沸点より低い沸点を有する
化合物（以下、蒸溜助剤ともいう。）の存在下に行い、
目的とする有機化合物を精製する。In the present invention, the distillation of the object to be purified is carried out in the presence of a compound having a boiling point lower than that of the target organic compound (hereinafter also referred to as a distillation aid),
Purify the desired organic compound.
【００２０】低温昇華性物質は、蒸留の初期に昇華し、
蒸留装置内部に凝固して付着する。蒸留助剤は、その沸
点に応じて低温昇華性物質の昇華と同時かまたは相前後
して留出し、蒸留装置内部に付着した低温昇華性物質を
洗い流すか、または、低温昇華性物質の蒸留装置内部へ
の付着を抑制する作用を有する。したがって、蒸留助剤
によって低温昇華性物質が排出された後に、留出する目
的とする有機化合物を回収することによって、目的とす
る有機化合物を高純度で回収することができる。The low-temperature sublimable substance sublimes at the beginning of distillation,
Solidifies and adheres inside the distillation apparatus. The distillation aid is distilled off at the same time as or before or after the sublimation of the low-temperature sublimable substance, depending on its boiling point, to wash out the low-temperature sublimable substance attached inside the distillation apparatus, or to distill the low-temperature sublimable substance. Has the effect of suppressing adhesion to the inside. Therefore, after the low-temperature sublimable substance is discharged by the distillation aid, the target organic compound to be distilled is recovered, whereby the target organic compound can be recovered with high purity.
【００２１】蒸留助剤は、目的とする有機化合物の沸点
よりも低い沸点を有するものであれば、どのような化合
物であってもよい。蒸留助剤の沸点は低温昇華性物質の
昇華開始温度以上であってもよく、また、未満であって
もよい。蒸留助剤の沸点が低温昇華性物質の昇華開始温
度以上であれば、低温昇華性物質の昇華と同時に、また
は昇華の後に蒸留助剤が留出し、留出する蒸留助剤によ
って蒸留装置内部に付着した低温昇華性物質を洗い流す
ことができる。蒸留助剤の沸点が低温昇華性物質の昇華
開始温度未満であっても、低温昇華性物質の昇華前に留
出する蒸留助剤によって低温昇華性物質の蒸留装置内部
への付着を防止することができる。その結果、目的化合
物を高純度で蒸溜することができる。The distillation aid may be any compound having a boiling point lower than the boiling point of the target organic compound. The boiling point of the distillation aid may be equal to or higher than the sublimation start temperature of the low-temperature sublimable substance, or may be lower. If the boiling point of the distillation aid is equal to or higher than the sublimation start temperature of the low-temperature sublimable substance, the distillation aid distills out simultaneously with or after the sublimation of the low-temperature sublimable substance and enters the distillation apparatus by the distilled distillation aid. The attached low-temperature sublimable substance can be washed away. Even if the boiling point of the distillation aid is lower than the sublimation start temperature of the low-temperature sublimable substance, the distillation aid distilled out before the sublimation of the low-temperature sublimable substance prevents the low-temperature sublimable substance from adhering to the inside of the distillation apparatus. Can be. As a result, the target compound can be distilled with high purity.
【００２２】蒸留助剤は、低温昇華性物質を溶解するも
のであることが、高純度の有機溶媒を高回収率で得るこ
とができるために好ましい。It is preferable that the distillation aid dissolves a low-temperature sublimable substance, since a high-purity organic solvent can be obtained at a high recovery rate.
【００２３】目的とする有機化合物との分離が容易な蒸
留助剤を用いた場合には、蒸留が進んで有機化合物が留
出し、蒸留助剤と混合した場合でも、蒸留助剤が容易に
取り除けるので有機化合物を高純度で得ることができ
る。例えば、有機化合物が水に不溶の場合、水溶性の蒸
留助剤を用いれば、留出液を水洗いすることにより容易
に有機化合物を得ることができる。また、有機化合物が
水、酸性水溶液、またはアルカリ性水溶液に易溶の場
合、非水溶性の蒸留助剤を用いることにより、留出液を
それぞれ水、酸性水溶液、またはアルカリ性水溶液に溶
解し、分液操作等により蒸留助剤を除いてから、必要に
応じて中和操作をし、水を取り除くことにより容易に有
機化合物を得ることができる。さらに、有機化合物が水
に不溶で、酸またはアルカリに安定であれば、酸性また
はアルカリ性の蒸留助剤を用いることもでき、この場合
にはそれぞれアルカリ性水溶液または酸性水溶液で洗浄
することにより容易に有機化合物を得ることができる。When a distillation aid which can be easily separated from the target organic compound is used, the distillation proceeds and the organic compound is distilled off. Even when the distillation aid is mixed with the distillation aid, the distillation aid can be easily removed. Therefore, an organic compound can be obtained with high purity. For example, when the organic compound is insoluble in water, the organic compound can be easily obtained by washing the distillate with water by using a water-soluble distillation aid. Further, when the organic compound is easily soluble in water, an acidic aqueous solution, or an alkaline aqueous solution, the distillate is dissolved in water, an acidic aqueous solution, or an alkaline aqueous solution, respectively, by using a water-insoluble distillation aid. The organic compound can be easily obtained by removing the distillation aid by an operation or the like, then performing a neutralization operation as necessary, and removing water. Furthermore, if the organic compound is insoluble in water and stable to acid or alkali, an acidic or alkaline distillation aid can be used. In this case, the organic compound can be easily washed by washing with an alkaline aqueous solution or an acidic aqueous solution, respectively. A compound can be obtained.
【００２４】蒸留助剤は、被精製物に含まれる有機化合
物及び低温昇華性物質の種類に応じて適宜決定すればよ
いが、カルボニル基を含有する化合物は、効率よく低温
昇華性物質の付着を抑制することが可能であり、被生成
物中の有機化合物の含有量が低い場合であっても、目的
とする有機化合物を高い純度で得ることが可能である。The distillation aid may be appropriately determined according to the type of the organic compound and the low-temperature sublimable substance contained in the object to be purified. The compound containing a carbonyl group can efficiently adhere the low-temperature sublimable substance. It is possible to suppress the generation of the target organic compound with high purity even when the content of the organic compound in the product is low.
【００２５】本発明において好適に使用できる蒸溜助剤
を具体的に例示すれば、例えば、ｎ−ブチルフェニルエ
ーテル、ジヘキシルエーテル等のエーテル類；ジエチレ
ングリコール、トリエチレングリコール、テトラエチレ
ングリコール、ジプロピレングリコール等のポリアルキ
レングリコール類；ジメチルスルホキシドやスルホラン
等のスルホキシドやスルホン類；ヘキサメチルりん酸ト
リアミド等のりん酸アミド類；ベンジルイソプロピルケ
トン、イソプロピルフェニルケトン、ヘプタノフェノ
ン、メチルシクロヘキサノン等の非環状または環状のケ
トン類；デカナール、ベンツアルデヒド等のアルデヒド
類；ジエチレングリコールジアセテート、フェニルアセ
テート等のエステル類；ジメチルホルムアミド、ジプロ
ピルホルムアミド、Ｎ−ベンジルアセトアミド、アセト
アニリド、１−ホルミルピペリジン、１−アセチルピペ
リジン、Ｎ−ホルミルモルホリン、Ｎ，Ｎ−ジエチルア
セトアセトアミド等の非環状のアミド類；イプシロン−
カプロラクタム、２−ピロリジノン、Ｎ−メチルピロリ
ジノン、１−メチル−２−ピロリドン、１−メチル−２
−ピペリドン、２−ピペリドン、２−ピロリドン、Ｎ−
メチル−４−ピペリドン等の環状アミド類；テトラエチ
ルウレア、１，３−ジエチルウレア、１，１−ジエチル
ウレア等の非環状のウレア類；１，３−ジメチル−２−
イミダゾリジノン、１，３−ジメチル−３，４，５，６
−テトラヒドロ−２（１Ｈ）−ピリミジノン、エチレン
ウレア、テトラヒドロ−２−ピリミジノン等の環状ウレ
ア類；フタルイミド、スクシンイミド等のイミド類；無
水シクロヘキサンジカルボン酸等の酸無水物類；カルバ
ミック酸メチルエステル等のウレタン類；ラクチド類；
等が挙げられる。これら蒸留助剤は単独で用いてもよい
し、複数種類を混合して用いてもよい。Specific examples of distillation aids that can be suitably used in the present invention include, for example, ethers such as n-butylphenyl ether and dihexyl ether; diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and the like. Polyalkylene glycols; sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane; phosphoric amides such as hexamethylphosphoric triamide; acyclic or cyclic ketones such as benzyl isopropyl ketone, isopropyl phenyl ketone, heptanophenone and methyl cyclohexanone Aldehydes such as decanal and benzaldehyde; esters such as diethylene glycol diacetate and phenylacetate; dimethylformamide, dipropylformamide; - benzylacetamide, acetanilide, 1-formyl-piperidine, 1-acetyl piperidine, N- formyl morpholine, N, acyclic amides such as N- diethyl acetoacetamide; epsilon -
Caprolactam, 2-pyrrolidinone, N-methylpyrrolidinone, 1-methyl-2-pyrrolidone, 1-methyl-2
-Piperidone, 2-piperidone, 2-pyrrolidone, N-
Cyclic amides such as methyl-4-piperidone; acyclic ureas such as tetraethylurea, 1,3-diethylurea, and 1,1-diethylurea; 1,3-dimethyl-2-
Imidazolidinone, 1,3-dimethyl-3,4,5,6
Cyclic ureas such as tetrahydro-2 (1H) -pyrimidinone, ethylene urea, and tetrahydro-2-pyrimidinone; imides such as phthalimide and succinimide; acid anhydrides such as cyclohexanedicarboxylic anhydride; urethanes such as methyl carbamic acid ester Lactides;
And the like. These distillation aids may be used alone or in combination of two or more.
【００２６】これらの蒸溜助剤のなかでも、下記一般式
（２）Among these distillation aids, the following general formula (2)
【００２７】[0027]
【化２】 Embedded image
【００２８】（式中、Ｒ1は水素原子又は炭素数１〜６
のアルキル基であり、Ａは−ＣＨ2−または＞Ｎ−Ｒ
2（Ｒ2は水素原子又は炭素数１〜６のアルキル基であ
る。）であり、ｎは１〜６の整数である。）で示される
環状ウレア類又は環状アミド類は、被精製物である粗有
機化合物に含まれる低温昇華性物質に対して特に良好な
溶解性を示すことから、目的とする有機化合物を高純
度、高回収率で得ることができ、特に好ましい。(Wherein, R 1 is a hydrogen atom or a carbon number of 1 to 6)
A is —CH 2 — or> NR.
2 (R 2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and n is an integer of 1 to 6. ), The cyclic ureas or cyclic amides show particularly good solubility in low-temperature sublimable substances contained in the crude organic compound to be purified, so that the target organic compound has high purity, It is particularly preferable because it can be obtained at a high recovery rate.
【００２９】前記一般式（１）において、Ｒ1、Ｒ2は共
に独立した水素原子又は炭素数１〜６のアルキル基であ
る。該アルキル基を具体的に例示すれば、メチル基、エ
チル基、プロピル基、ブチル基、ヘキシル基等の直鎖ア
ルキル基；及びイソプロピル基、第３級ブチル基、ネオ
ペンチル基等の分岐アルキル基が挙げられる。In the general formula (1), R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group and hexyl group; and branched alkyl groups such as isopropyl group, tertiary butyl group and neopentyl group. No.
【００３０】特に好ましい蒸留助剤を具体的に例示すれ
ば、イプシロン−カプロラクタム、２−ピロリジノン、
Ｎ−メチルピロリジノン、１−メチル−２−ピロリド
ン、１−メチル−２−ピペリドン、２−ピペリドン、２
−ピロリドン、Ｎ−メチル−４−ピペリドン等の環状ア
ミド類；１，３−ジメチル−２−イミダゾリジノン、
１，３−ジメチル−３，４，５，６−テトラヒドロ−２
（１Ｈ）−ピリミジノン、エチレンウレア、テトラヒド
ロ−２−ピリミジノン等の環状ウレア類を挙げることが
できる。Specific examples of particularly preferred distillation aids include epsilon-caprolactam, 2-pyrrolidinone,
N-methylpyrrolidinone, 1-methyl-2-pyrrolidone, 1-methyl-2-piperidone, 2-piperidone, 2
Cyclic amides such as -pyrrolidone and N-methyl-4-piperidone; 1,3-dimethyl-2-imidazolidinone;
1,3-dimethyl-3,4,5,6-tetrahydro-2
Cyclic ureas such as (1H) -pyrimidinone, ethylene urea, and tetrahydro-2-pyrimidinone.
【００３１】蒸留助剤の存在のさせ方は、目的とする有
機化合物が沸騰を開始する前に、昇華して蒸留装置内部
に付着した低温昇華性物質を洗い流せるか、または低温
昇華性物質の蒸留装置内部への付着を防止できるような
態様であれば特に限定されない。例えば、蒸留を開始す
る前に蒸留助剤を予め被精製物と混合しても良いし、蒸
留を開始してから蒸留釜に直接、或いは蒸留塔、蒸留
管、乾留ラインに供給してもよい。[0031] The method of making the distillation aid exist is that the sublimation allows the low-temperature sublimable substance attached to the interior of the distillation apparatus to be washed away before the target organic compound starts boiling, or that the low-temperature sublimable substance is distilled. There is no particular limitation as long as it can prevent adhesion to the inside of the device. For example, a distillation aid may be mixed in advance with the substance to be purified before starting distillation, or may be supplied directly to a distillation still after starting distillation, or to a distillation column, a distillation tube, or a carbonization line. .
【００３２】なお、蒸留助剤の効果としては、前記した
低温昇華性物質の洗浄効果の他に、例えば、蒸留助剤を
添加して被精製物の粘度を下げたり、有機化合物が常温
で固体である場合には、溶液化や懸濁液化したりするこ
とにより取扱を容易にする効果もある。さらに蒸留操作
中（特に留出液を冷却するときに）に固体が析出するこ
となく効率よく蒸留精製を行うことが出来るようになる
という効果も期待できる。前記洗浄効果の他にこの様な
効果を期待する場合には、有機化合物の沸点に近い沸点
を持つ液体を第二の蒸留助剤として被精製物に添加する
のが好適である。The effects of the distillation aid include, in addition to the above-described cleaning effect of the low-temperature sublimable substance, for example, the addition of a distillation aid to lower the viscosity of the object to be purified or the solidification of the organic compound at room temperature. In the case of, there is also an effect of facilitating handling by forming a solution or a suspension. In addition, an effect can be expected that distillation can be efficiently performed without depositing solids during the distillation operation (particularly when the distillate is cooled). When such an effect is expected in addition to the washing effect, it is preferable to add a liquid having a boiling point close to the boiling point of the organic compound as a second distillation aid to the object to be purified.
【００３３】蒸留助剤の添加量は、低温昇華性物質が蒸
留装置から全て洗い流されるに必要十分な量を加えれば
よく、不純物の量や蒸留助剤への溶解性等を勘案して加
える量を決定すれば良いが、通常は、被精製物中に含ま
れる低温昇華性物質１重量部に対して０．１〜１００重
量部、好ましくは１〜２０重量部の範囲である。The amount of the distillation aid to be added may be an amount that is necessary and sufficient for all the low-temperature sublimable substance to be washed away from the distillation apparatus, and is added in consideration of the amount of impurities, solubility in the distillation aid, and the like. The amount is usually 0.1 to 100 parts by weight, preferably 1 to 20 parts by weight, per 1 part by weight of the low-temperature sublimable substance contained in the object to be purified.
【００３４】本発明の製造方法において、蒸留助剤の存
在下での蒸留方式は特に限定されず、単蒸留または分別
蒸留が用いられ、分別蒸留の場合、分留管としては、ビ
グルー型、同心円筒型、回転バンド型、充填カラム等の
薄膜式分留管や泡鐘型、多孔板型等のプレート式分留管
が好適に用いられ、特に減圧蒸留を行う場合は圧力損失
の少ない薄膜式分留管が好適に用いられる。また、クー
ゲルロールや薄膜蒸留等の公知の蒸留方式が何ら制限無
く採用できる。また、温度や圧力、還流比などの蒸留条
件も特に限定されず、被精製物の組成、蒸留助剤の種類
及び添加量、最終的に得られる有機化合物の純度等に応
じて適宜決定すればよい。In the production method of the present invention, the distillation method in the presence of a distillation aid is not particularly limited, and simple distillation or fractional distillation is used. Thin-film fractionating tubes such as cylindrical, rotating band, and packed columns, and plate-type fractionating tubes such as bubble-bell type and perforated plate type are preferably used. A fractionating tube is preferably used. In addition, known distillation methods such as Kugelrohr and thin-film distillation can be adopted without any limitation. The distillation conditions such as temperature, pressure, and reflux ratio are not particularly limited, and may be appropriately determined according to the composition of the product to be purified, the type and amount of the distillation aid, the purity of the finally obtained organic compound, and the like. Good.
【００３５】[0035]
【実施例】以下に実施例および比較例を掲げて本発明を
さらに詳細に述べるが、本発明はこれらの実施例によっ
て何ら制限されるものではない。The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples.
【００３６】実施例１ 昇華性の不純物としてアダマンタン（昇華開始温度、室
温以下）２．１重量％、２−メチレンアダマンタン（昇
華開始温度３０℃）５．３重量％、２−アダマンタノン
（昇華開始温度５０℃）４．５重量％、２−メチル−２
−アダマンタノール（昇華開始温度６０℃）１．２重量
％を含む純度７２重量％の２−メチル−２−アダマンチ
ルメタクリレート（沸点９２℃／０．３ｍｍＨｇ）１重
量部に、０．０５重量部の１，３−ジメチル−２−イミ
ダゾリジノン（沸点２２５℃）を加え、減圧下蒸留を行
った。Example 1 Adamantane (sublimation start temperature, room temperature or less) 2.1% by weight, 2-methylene adamantane (sublimation start temperature 30 ° C.) 5.3% by weight, 2-adamantanone (sublimation start) as sublimable impurities 4.5% by weight, 2-methyl-2
0.05 parts by weight of 1 part by weight of 2-methyl-2-adamantyl methacrylate (boiling point: 92 ° C./0.3 mmHg) having a purity of 72% by weight containing 1.2% by weight of adamantanol (sublimation starting temperature: 60 ° C.) 1,3-Dimethyl-2-imidazolidinone (boiling point: 225 ° C.) was added, and distillation was performed under reduced pressure.
【００３７】蒸留は、５ｃｍのビグルー型分留管と全縮
型還流分留装置を用い、ガラスキャピラリーで空気を導
入しながら、真空度０．３ｍｍＨｇで行った。初めに不
純物として混入していたアダマンタン等は蒸留装置にわ
ずかに付着したが、１，３−ジメチル−２−イミダゾリ
ジノンが留出するにつれて徐々に溶解、剥離して、閉塞
等を起こさなかった。初留をカットし、２−メチル−２
−アダマンチルメタクリレートが留出し始めた時点で本
留を取りはじめた。本留分を集めたところ２−メチル−
２−アダマンチルメタクリレートを純度９７．７重量％
で得ることができた。The distillation was carried out at a degree of vacuum of 0.3 mmHg using a 5 cm Vigreux-type fractionating tube and a fully condensed reflux fractionating device while introducing air through a glass capillary. Adamantane and the like initially mixed as impurities adhered slightly to the distillation apparatus, but gradually dissolved and peeled off as 1,3-dimethyl-2-imidazolidinone was distilled off, and did not cause blockage or the like. . Cut the first distillate, 2-methyl-2
When the adamantyl methacrylate began to distill, the main distillation was started. When the main fraction was collected, 2-methyl-
2-adamantyl methacrylate having a purity of 97.7% by weight
Could be obtained.
【００３８】実施例２ 実施例１において蒸留助剤として用いた１，３−ジメチ
ル−２−イミダゾリジノンの代わりにＮ−メチルピロリ
ジノン（沸点８１℃／１０ｍｍＨｇ）を０．３重量部用
いた他は実施例１に準じて蒸留を行った。初めに蒸留装
置内に付着した昇華性不純物は、Ｎ−メチルピロリジノ
ンが留出するにつれて徐々に溶解、剥離して、閉塞等を
起こさなかった。本留において２−メチル−２−アダマ
ンチルメタクリレートの留出と共にＮ−メチルピロリジ
ノンは混ざり合ってしまったが、留出液を純水で洗浄す
ることにより、２−メチル−２−アダマンチルメタクリ
レートを純度９５．８重量％で得ることができた。Example 2 In place of 1,3-dimethyl-2-imidazolidinone used as a distillation aid in Example 1, 0.3 part by weight of N-methylpyrrolidinone (boiling point 81 ° C./10 mmHg) was used. Was distilled according to Example 1. The sublimable impurities initially attached to the distillation apparatus were gradually dissolved and peeled off as N-methylpyrrolidinone was distilled off, and did not cause blockage or the like. In this distillation, N-methylpyrrolidinone was mixed with 2-methyl-2-adamantyl methacrylate while distilling off 2-methyl-2-adamantyl methacrylate. By washing the distillate with pure water, 2-methyl-2-adamantyl methacrylate was purified to a purity of 95%. 0.8% by weight.
【００３９】実施例３ 昇華性の不純物としてアダマンタン６．３重量％、２−
アダマンタノン２．１重量％、２−エチル−２−アダマ
ンタノール（昇華開始温度６０℃）０．９重量％含む純
度８２重量％の２−エチル−２−アダマンチルメタクリ
レート（沸点９６℃／０．２ｍｍＨｇ）１重量部に対
し、０．１重量部のテトラエチルウレア（沸点２１４
℃）と０．１重量部の１，３−ジメチル−３，４，５，
６−テトラヒドロ−２（１Ｈ）−ピリミジノン（沸点２
３２℃）を加え、減圧下蒸留を行った。Example 3 As a sublimable impurity, 6.3% by weight of adamantane, 2-
82% by weight of 2-ethyl-2-adamantyl methacrylate (boiling point: 96 ° C./0.2 mmHg) containing 2.1% by weight of adamantanone and 0.9% by weight of 2-ethyl-2-adamantanol (sublimation start temperature: 60 ° C.) ) 0.1 part by weight of tetraethylurea (boiling point 214 parts
° C) and 0.1 parts by weight of 1,3-dimethyl-3,4,5,
6-tetrahydro-2 (1H) -pyrimidinone (boiling point 2
32 ° C.) and distilled under reduced pressure.
【００４０】蒸留は、５ｃｍのビグルー型分留管と全縮
型還流分留装置を用い、ガラスキャピラリーで空気を導
入しながら、真空度０．２ｍｍＨｇで減圧蒸留した。The distillation was carried out under reduced pressure at a vacuum of 0.2 mmHg using a 5 cm Vigreux-type fractionating tube and a fully condensed reflux fractionating device while introducing air through a glass capillary.
【００４１】その結果、蒸留装置内に固体が析出するこ
となく蒸留は進行し、本留の留出液をヘキサンに溶解
し、純水で洗浄した後にヘキサンを留去することにより
２−エチル−２−アダマンチルメタクリレートを純度９
６．５重量％で得ることができた。なお、この２−エチ
ル−２−アダマンチルメタクリレートを室温で放置する
と結晶になった。As a result, the distillation proceeded without depositing a solid in the distillation apparatus, and the distillate of the main distillate was dissolved in hexane, washed with pure water, and then hexane was distilled off to remove 2-ethyl-distillate. 2-adamantyl methacrylate with a purity of 9
6.5% by weight could be obtained. The 2-ethyl-2-adamantyl methacrylate crystallized when left at room temperature.
【００４２】実施例４ 昇華性の不純物としてアダマンタン５．１重量％、２−
アダマンタノン１．１重量％、２−ブチル−２−アダマ
ンタノール（昇華開始温度７０℃）０．４重量％を含む
純度７９重量％の２−ブチル−２−アダマンチルメタク
リレート（沸点１０３℃／０．２ｍｍＨｇ）１重量部に
対し、０．１重量部の１，３−ジメチル−３，４，５，
６−テトラヒドロ−２（１Ｈ）−ピリミジノン（沸点２
３２℃）を加え、実施例３と同様にして減圧下蒸留を行
った。Example 4 5.1% by weight of adamantane as a sublimable impurity, 2-
2-butyl-2-adamantyl methacrylate having a purity of 79% by weight, containing 1.1% by weight of adamantanone and 0.4% by weight of 2-butyl-2-adamantanol (sublimation starting temperature: 70 ° C.) (boiling point: 103 ° C./0.1° C.). 2 mmHg) 1 part by weight, 0.1 part by weight of 1,3-dimethyl-3,4,5,5
6-tetrahydro-2 (1H) -pyrimidinone (boiling point 2
32 ° C.), and the mixture was distilled under reduced pressure in the same manner as in Example 3.
【００４３】その結果、蒸留装置内に固体が析出するこ
となく蒸留は進行し、本留の留出液をヘキサンに溶解
し、純水で洗浄し、続いてヘキサンを留去することによ
り２−ブチル−２−アダマンチルメタクリレートを純度
９７．５重量％で得ることができた。As a result, the distillation proceeds without depositing a solid in the distillation apparatus, and the distillate of the main distillate is dissolved in hexane, washed with pure water, and then hexane is distilled off. Butyl-2-adamantyl methacrylate could be obtained with a purity of 97.5% by weight.
【００４４】実施例５ 昇華性の不純物としてアダマンタン（昇華開始温度、室
温以下）０．０５重量％、２−アダマンタノン（昇華開
始温度５０℃）２．５重量％、２−メチル−２−アダマ
ンタノール（昇華開始温度６０℃）３．８重量％を含む
純度７８重量％の２−メチル−２−アダマンチルメタク
リレート（沸点９２℃／０．３ｍｍＨｇ）１重量部に、
０．１重量部のジエチレングリコール（沸点２４５℃）
を加え、減圧下蒸留を行った。Example 5 As a sublimable impurity, adamantane (sublimation starting temperature, room temperature or lower) 0.05% by weight, 2-adamantanone (sublimation starting temperature 50 ° C.) 2.5% by weight, 2-methyl-2-adaman To 1 part by weight of 2-methyl-2-adamantyl methacrylate (boiling point: 92 ° C./0.3 mmHg) containing 3.8% by weight of tanol (sublimation start temperature: 60 ° C.) and having a purity of 78% by weight,
0.1 parts by weight of diethylene glycol (boiling point: 245 ° C)
And distilled under reduced pressure.
【００４５】蒸留は、５ｃｍのビグルー型分留管と全縮
型還流分留装置を用い、ガラスキャピラリーで空気を導
入しながら、真空度０．３ｍｍＨｇで減圧蒸留した。初
めに不純物として混入していた２−アダマンタノンや２
−メチル−２−アダマンタノールが昇華して蒸留装置の
壁に付着したが、ジエチレングリコールが留出するにつ
れて徐々に溶解、剥離して、閉塞等を起こさなかった。
初留をカットし、２−メチル−２−アダマンチルメタク
リレートが留出し始めた時点で本留を取りはじめたとこ
ろ、ジエチレングリコールは２−メチル−２−アダマン
チルメタクリレートと混ざり合わず、ジエチレングリコ
ールが下層に分離した。これを分液することにより２−
メチル−２−アダマンチルメタクリレートを純度９７．
６重量％で得ることができた。The distillation was carried out under reduced pressure at a degree of vacuum of 0.3 mmHg using a 5 cm Vigreux-type fractionating tube and a fully condensed reflux fractionating device while introducing air through a glass capillary. 2-adamantanone and 2 which were initially mixed as impurities
-Methyl-2-adamantanol sublimated and adhered to the wall of the distillation apparatus, but gradually dissolved and peeled off as diethylene glycol was distilled off, and did not cause blockage or the like.
When the first distillation was cut and the main distillation was started at the time when 2-methyl-2-adamantyl methacrylate began to distill, diethylene glycol was not mixed with 2-methyl-2-adamantyl methacrylate, and diethylene glycol was separated into a lower layer. . By separating this, 2-
The purity of methyl-2-adamantyl methacrylate is 97.
6% by weight could be obtained.
【００４６】実施例６ 実施例５において蒸留助剤として用いたジエチレングリ
コールの代わりにＮ−メチルピロリジノン（沸点８１℃
／１０ｍｍＨｇ）を用いた他は実施例５に準じて蒸留を
行った。初めに蒸留装置内に付着した昇華性不純物は、
Ｎ−メチルピロリジノンが留出するにつれて徐々に溶
解、剥離して、閉塞等を起こさなかった。本留において
２−メチル−２−アダマンチルメタクリレートの留出と
共にＮ−メチルピロリジノンは混ざり合ってしまった
が、留出液を純水で洗浄することにより、２−メチル−
２−アダマンチルメタクリレートを純度９７．０重量％
で得ることができた。Example 6 Instead of diethylene glycol used as a distillation aid in Example 5, N-methylpyrrolidinone (boiling point: 81 ° C.)
/ 10 mmHg), except that distillation was carried out in the same manner as in Example 5. The sublimable impurities that first adhered to the distillation apparatus
As N-methylpyrrolidinone was distilled off, it gradually dissolved and peeled off, and no clogging or the like occurred. In this distillation, N-methylpyrrolidinone was mixed with the distillation of 2-methyl-2-adamantyl methacrylate, but the distillate was washed with pure water to give 2-methyl-pyrrolidinone.
2-adamantyl methacrylate having a purity of 97.0% by weight
Could be obtained.
【００４７】実施例７ 昇華性の不純物としてアダマンタン０．２重量％、２−
アダマンタノン２．０重量％、２−エチル−２−アダマ
ンタノール（昇華開始温度６０℃）０．８重量％含む純
度８６重量％の２−エチル−２−アダマンチルメタクリ
レート（沸点９６℃／０．２ｍｍＨｇ）１重量部に対
し、０．１重量部のジエチレングリコール（沸点２４５
℃）と０．１重量部のテトラエチレングリコール（沸点
３１４℃）を加え、減圧下蒸留を行った。Example 7 As a sublimable impurity, adamantane 0.2% by weight, 2-
86% by weight of 2-ethyl-2-adamantyl methacrylate (boiling point: 96 ° C./0.2 mmHg) containing 2.0% by weight of adamantanone and 0.8% by weight of 2-ethyl-2-adamantanol (sublimation start temperature: 60 ° C.) ) Per part by weight of 0.1 part by weight of diethylene glycol (boiling point 245)
° C) and 0.1 parts by weight of tetraethylene glycol (boiling point: 314 ° C) and distilled under reduced pressure.
【００４８】蒸留は、５ｃｍのビグルー型分留管と全縮
型還流分留装置を用い、ガラスキャピラリーで空気を導
入しながら、真空度０．２ｍｍＨｇで減圧蒸留した。The distillation was carried out under reduced pressure at a vacuum of 0.2 mmHg while introducing air through a glass capillary using a 5 cm Vigreux-type fractionating tube and a fully condensed reflux fractionating apparatus.
【００４９】その結果、蒸留装置内に固体が析出するこ
となく蒸留は進行し、本留留出液をヘキサンに溶解し、
純水で洗浄した後にヘキサンを留去することにより２−
エチル−２−アダマンチルメタクリレートを純度９６．
３重量％で得ることができた。なお、この２−エチル−
２−アダマンチルメタクリレートを室温で放置すると結
晶になった。As a result, the distillation proceeds without depositing a solid in the distillation apparatus, and the distillate is dissolved in hexane.
After washing with pure water and distilling off hexane, 2-
Ethyl-2-adamantyl methacrylate has a purity of 96.
3% by weight could be obtained. This 2-ethyl-
The 2-adamantyl methacrylate crystallized when left at room temperature.
【００５０】実施例８ 昇華性の不純物としてアダマンタン０．１重量％、２−
アダマンタノン１．０重量％、２−ブチル−２−アダマ
ンタノール（昇華開始温度７０℃）０．５重量％を含む
純度８５重量％の２−ブチル−２−アダマンチルメタク
リレート（沸点１０３℃／０．２ｍｍＨｇ）１重量部に
対し、０．１重量部のテトラエチレングリコール（沸点
３１４℃）を加え、実施例７と同様にして減圧下蒸留を
行った。Example 8 As a sublimable impurity, adamantane 0.1% by weight, 2-
2-butyl-2-adamantyl methacrylate having a purity of 85% by weight and containing 1.0% by weight of adamantanone and 0.5% by weight of 2-butyl-2-adamantanol (sublimation starting temperature: 70 ° C) (boiling point: 103 ° C / 0. 0.1 parts by weight of tetraethylene glycol (boiling point: 314 ° C.) was added to 1 part by weight of 2 mmHg), and distillation was performed under reduced pressure in the same manner as in Example 7.
【００５１】その結果、蒸留装置内に固体が析出するこ
となく蒸留は進行し、本留の留出液をヘキサンに溶解
し、純水で洗浄し、続いてヘキサンを留去することによ
り２−ブチル−２−アダマンチルメタクリレートを純度
９７．５重量％で得ることができた。As a result, the distillation proceeds without depositing a solid in the distillation apparatus, and the distillate of the main distillate is dissolved in hexane, washed with pure water, and then hexane is distilled off. Butyl-2-adamantyl methacrylate could be obtained with a purity of 97.5% by weight.
【００５２】実施例９ 昇華性の不純物としてアダマンタン（昇華開始温度、室
温以下）０．１重量％、２−メチレンアダマンタン（昇
華開始温度４０℃）１２．４重量％、２−アダマンタノ
ン（昇華開始温度５０℃）６．３重量％、２−メチル−
２−アダマンタノール（昇華開始温度６０℃）２．７重
量％を含む純度６５重量％の２−メチル−２−アダマン
チルメタクリレート（沸点９２℃／０．３ｍｍＨｇ）１
重量部に、０．１重量部の１，３−ジメチル−２−イミ
ダゾリジノン（沸点２２５℃）を加え、減圧下蒸留を行
った。Example 9 As a sublimable impurity, 0.1% by weight of adamantane (sublimation start temperature, room temperature or less), 12.4% by weight of 2-methylene adamantane (sublimation start temperature of 40 ° C.), and 2-adamantanone (sublimation start temperature) 6.3% by weight, 2-methyl-
2-Methyl-2-adamantyl methacrylate (boiling point 92 ° C./0.3 mmHg) 1 containing 2.7% by weight of 2-adamantanol (sublimation starting temperature 60 ° C.) 1
0.1 parts by weight of 1,3-dimethyl-2-imidazolidinone (boiling point: 225 ° C.) was added to parts by weight, and distillation was performed under reduced pressure.
【００５３】蒸留は、５ｃｍのビグルー型分留管と全縮
型還流分留装置を用い、ガラスキャピラリーで空気を導
入しながら、真空度０．３ｍｍＨｇで行った。初めに不
純物として混入していたアダマンタン等は昇華して一部
蒸留装置の壁に付着したが、１，３−ジメチル−２−イ
ミダゾリジノンが留出するにつれて徐々に溶解、剥離し
て、閉塞等を起こさなかった。初留をカットし、２−メ
チル−２−アダマンチルメタクリレート純度が８０％を
越えた時点で本留を取りはじめた。本留分を集めたとこ
ろ２−メチル−２−アダマンチルメタクリレートを純度
９７．７重量％で得ることができた。The distillation was carried out at a degree of vacuum of 0.3 mmHg while using a 5 cm Vigreux type fractionating tube and a fully condensing reflux fractionating device while introducing air through a glass capillary. Adamantane and the like initially mixed as impurities were sublimated and partially adhered to the wall of the distillation apparatus, but gradually dissolved and peeled off as 1,3-dimethyl-2-imidazolidinone was distilled off, and clogged. Did not occur. The first distillation was cut, and the main distillation was started when the purity of 2-methyl-2-adamantyl methacrylate exceeded 80%. When this fraction was collected, 2-methyl-2-adamantyl methacrylate was obtained with a purity of 97.7% by weight.
【００５４】実施例１０〜１９ 実施例９において蒸留助剤として用いた１，３−ジメチ
ル−２−イミダゾリジノンの代わりに表１に示す各種蒸
留助剤を用いた他は実施例９に準じて蒸留を行った。本
留分に蒸留助剤が混合している場合には、本留留出液を
ヘキサンに溶解し、純水で洗浄した後にヘキサンを留去
することにより目的物を得た。Examples 10 to 19 The procedure of Example 9 was repeated except that the various distillation aids shown in Table 1 were used in place of 1,3-dimethyl-2-imidazolidinone used as the distillation aid in Example 9. Distillation. When a distillation aid was mixed with the main distillate, the distillate was dissolved in hexane, washed with pure water, and then the hexane was distilled off to obtain the desired product.
【００５５】[0055]
【表１】 [Table 1]
【００５６】結果を併せて表１に示す。低温昇華性物質
が多量に含まれている場合においてもカルボニル基を含
有する化合物を蒸留助剤として用いた場合には効果的に
低温昇華性物質の付着を抑制することが可能であった。Table 1 also shows the results. Even when the low-temperature sublimable substance was contained in a large amount, it was possible to effectively suppress the adhesion of the low-temperature sublimable substance when the compound having a carbonyl group was used as a distillation aid.
【００５７】比較例１ 実施例１で用いた純度７９重量％の２−メチル−２−ア
ダマンチルメタクリレートに何も加えずにそのまま減圧
蒸留を行ったところ、蒸留装置の冷却管が昇華性固体で
閉塞し、蒸留できなかった。Comparative Example 1 The 2-methyl-2-adamantyl methacrylate having a purity of 79% by weight used in Example 1 was subjected to vacuum distillation without any addition, and the cooling pipe of the distillation apparatus was clogged with a sublimable solid. And could not be distilled.
【００５８】比較例２ 実施例９で用いた純度６５重量％の２−メチル−２−ア
ダマンチルメタクリレートに何も加えずにそのまま減圧
蒸留を行ったところ、蒸留装置の冷却管が昇華性固体で
閉塞し、蒸留できなかった。COMPARATIVE EXAMPLE 2 The 2-methyl-2-adamantyl methacrylate having a purity of 65% by weight used in Example 9 was subjected to vacuum distillation without any addition, and the cooling pipe of the distillation apparatus was clogged with a sublimable solid. And could not be distilled.
【００５９】[0059]
【発明の効果】本発明の製造方法によれば、蒸溜の初期
に昇華して配管などに付着する昇華性物質を、昇華性物
質の昇華と同時に、またはそれに続いて留出する蒸留助
剤によって溶解または剥離させることができ、配管の閉
塞や有機化合物への溶解を避けることができる。また有
機化合物に蒸留助剤が混入しても容易に除去可能である
ことから、効率よく有機化合物を蒸留精製することが可
能となる。According to the production method of the present invention, a sublimable substance which sublimates at the beginning of distillation and adheres to a pipe or the like is removed by a distillation aid which is distilled simultaneously with or after the sublimation of the sublimable substance. It can be dissolved or peeled off, and it is possible to avoid clogging of the piping and dissolution in organic compounds. In addition, since the organic compound can be easily removed even if a distillation assistant is mixed, the organic compound can be efficiently distilled and purified.
【００６０】本発明により、これまで蒸留精製が困難で
あった昇華性物質を不純物として含む高沸点化合物を容
易に蒸留精製することが可能になった。本発明の製造方
法を採用することにより、半導体用レジスト材料として
の用途が期待される高純度アルキルアダマンチルエステ
ルを容易に得ることも可能である。According to the present invention, a high-boiling compound containing a sublimable substance as an impurity which has been difficult to purify by distillation can be easily purified by distillation. By employing the production method of the present invention, a high-purity alkyl adamantyl ester expected to be used as a resist material for semiconductors can be easily obtained.
Claims (1)
度で昇華する昇華性物質を不純物として含む粗有機化合
物を蒸留して高純度有機化合物を製造する方法におい
て、該有機化合物の沸点より低い沸点を有する化合物の
存在下に該蒸溜を行ない、該有機化合物の沸点より低い
沸点を有する化合物の留出により、昇華して蒸留装置内
部に付着した昇華性物質を洗い落とすか、または、昇華
性物質の蒸留装置内部への付着を防ぎ、次いで留出する
該有機化合物を回収することを特徴とする高純度有機化
合物の製造方法。1. A method for producing a high-purity organic compound by distilling a crude organic compound containing as an impurity a sublimable substance which sublimates at a temperature lower than the boiling point of the target organic compound, wherein the boiling point is lower than the boiling point of the organic compound. The distillation is carried out in the presence of a compound having the following formula: and the compound having a boiling point lower than the boiling point of the organic compound is distilled off, whereby the sublimable substance that has sublimated and adhered to the inside of the distillation apparatus is washed out, or the sublimable substance is removed. A method for producing a high-purity organic compound, comprising preventing adhesion to the inside of a distillation apparatus, and recovering the organic compound that is distilled off.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000149636A JP3998892B2 (en) | 1999-07-29 | 2000-05-22 | Method for producing high-purity alkyladamantyl ester |
| PCT/JP2001/000542 WO2001090033A1 (en) | 2000-05-22 | 2001-01-26 | Process for preparation of high-purity organic compounds |
| KR1020027014764A KR100649411B1 (en) | 2000-05-22 | 2001-01-26 | Process for preparation of high-purity organic compounds |
| EP01980029A EP1284252A4 (en) | 2000-05-22 | 2001-01-26 | Process for preparation of high-purity organic compounds |
| US10/296,319 US6852885B2 (en) | 2000-05-22 | 2001-01-26 | Production method of high purity organic compound |
| CNB018099548A CN1296332C (en) | 2000-05-22 | 2001-01-26 | Process for preparation of high-purity organic compounds |
| TW090101975A TWI245030B (en) | 2000-05-22 | 2001-01-29 | Production method of high purity alkyladamanthylester |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-214567 | 1999-07-29 | ||
| JP21456799 | 1999-07-29 | ||
| JP2000149636A JP3998892B2 (en) | 1999-07-29 | 2000-05-22 | Method for producing high-purity alkyladamantyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001097893A true JP2001097893A (en) | 2001-04-10 |
| JP3998892B2 JP3998892B2 (en) | 2007-10-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000149636A Expired - Fee Related JP3998892B2 (en) | 1999-07-29 | 2000-05-22 | Method for producing high-purity alkyladamantyl ester |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001090045A1 (en) * | 2000-05-22 | 2001-11-29 | Tokuyama Corporation | Process of the preparation of high-purity alkyladamantyl esters |
| JP2003073334A (en) * | 2001-09-04 | 2003-03-12 | Tokuyama Corp | 2-ethyl-2-adamantyl methacrylate crystal powder |
| JP2005002073A (en) * | 2003-06-16 | 2005-01-06 | Mitsubishi Chemicals Corp | Production method for 2-methyladamantan-2-yl (meth)acrylate and its purification method |
| WO2006018902A1 (en) * | 2004-08-19 | 2006-02-23 | Mitsubishi Chemical Corporation | Process for producing 2-methyladamantan-2-yl (meth)acrylate and 2-methyladamantan-2-yl (meth)acrylate |
| JP2007231011A (en) * | 2006-02-02 | 2007-09-13 | Showa Denko Kk | Method of azeotropic distillation |
-
2000
- 2000-05-22 JP JP2000149636A patent/JP3998892B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001090045A1 (en) * | 2000-05-22 | 2001-11-29 | Tokuyama Corporation | Process of the preparation of high-purity alkyladamantyl esters |
| US6696595B2 (en) | 2000-05-22 | 2004-02-24 | Tokuyama Corporation | Process of the preparation of high-purity alkyladamantyl esters |
| JP2003073334A (en) * | 2001-09-04 | 2003-03-12 | Tokuyama Corp | 2-ethyl-2-adamantyl methacrylate crystal powder |
| JP2005002073A (en) * | 2003-06-16 | 2005-01-06 | Mitsubishi Chemicals Corp | Production method for 2-methyladamantan-2-yl (meth)acrylate and its purification method |
| WO2006018902A1 (en) * | 2004-08-19 | 2006-02-23 | Mitsubishi Chemical Corporation | Process for producing 2-methyladamantan-2-yl (meth)acrylate and 2-methyladamantan-2-yl (meth)acrylate |
| JP2007231011A (en) * | 2006-02-02 | 2007-09-13 | Showa Denko Kk | Method of azeotropic distillation |
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| Publication number | Publication date |
|---|---|
| JP3998892B2 (en) | 2007-10-31 |
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