JPH0635412B2 - Method for producing hemiacetal compound - Google Patents
Method for producing hemiacetal compoundInfo
- Publication number
- JPH0635412B2 JPH0635412B2 JP29432988A JP29432988A JPH0635412B2 JP H0635412 B2 JPH0635412 B2 JP H0635412B2 JP 29432988 A JP29432988 A JP 29432988A JP 29432988 A JP29432988 A JP 29432988A JP H0635412 B2 JPH0635412 B2 JP H0635412B2
- Authority
- JP
- Japan
- Prior art keywords
- tfa
- compound
- hemiacetal compound
- mol
- ethanol
- 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.)
- Expired - Lifetime
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 [産業上の利用分野] 本発明は、医薬,農薬の中間原料として有用なトリフル
オロアセトアルデヒドを安定的に保存するためにヘミア
セタール化合物に変換する方法,または化合物自体とし
ても医薬,農薬の中間体として有用なヘミアセタール化
合物の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a method for converting trifluoroacetaldehyde, which is useful as an intermediate raw material for medicines and agricultural chemicals, into a hemiacetal compound for stable storage, or as a compound itself. Also relates to a method for producing a hemiacetal compound useful as an intermediate for medicines and agricultural chemicals.
[従来技術とその解決しようとする課題] トリフルオロアセトアルデヒド(以下、TFAと略す。)
は、分解,重合反応を起こし易い不安定な物質である。
通常は取扱が容易なTFA-2H2Oとして運搬,貯蔵される
が、長期間の保存中しばしば不溶物を生成する。[Conventional Technology and Problems to Be Solved] Trifluoroacetaldehyde (hereinafter abbreviated as TFA)
Is an unstable substance that is easily decomposed and polymerized.
Usually, it is transported and stored as TFA-2H 2 O which is easy to handle, but it often forms insoluble matter during long-term storage.
一般に、反応性の高いカルボニル基を有する化合物は、
安定化のためgem−ジオール化,ヘミアセタール化(カ
ルボニル基の保護)することが行われている。gem−ジ
オールとして表わすことのできるTFA・H2Oのヘミアセタ
ール化は下式のように可逆的に進行する。Generally, a compound having a highly reactive carbonyl group is
For stabilization, gem-diolation and hemiacetalization (protection of carbonyl group) have been performed. The hemiacetalization of TFA · H 2 O, which can be represented as a gem-diol, proceeds reversibly as shown in the following formula.
従来の方法としては、gem−ジオール化合物であるTFA-H
2Oを等モルの水に溶解して得られるTFA-2H2Oのエチルヘ
ミアセタール化が挙げられる。 The conventional method is TFA-H which is a gem-diol compound.
An example is TFA-2H 2 O obtained by dissolving 2 O in equimolar water to form ethyl hemiacetal.
TFA-2H2Oのエチルヘミアセタール化は、エタノールを1
倍当量以上添加することにより、平衡反応的に約67モル
%まで進行する。一方、エタノールと水が共沸組成C2H5
OH/H2O(モル比)=89.5/10.5を持つことを利用して、
エタノール大過剰で蒸留を行えば水の除去ができ、TFA
からのエチルヘミアセタール化合物(以下、TFA-EtOHと
略す。)を容易に生成することができる。このTFA-EtOH
はエタノールと沸点103℃で共沸し、共沸組成TFA-EtOH/
EtOH(モル比)=82/12のものが留分として得られるこ
とが知られている。[Chemische Berichte 106.2967(19
73)] しかし、この方法ではエタノールを大過剰必要とするだ
けでなく、処理後のエタノールの脱水設備に多大のコス
トがかかる。Ethyl hemiacetalization of TFA-2H 2 O converts ethanol to 1
By adding more than double equivalent, the reaction proceeds in an equilibrium reaction to about 67 mol%. On the other hand, ethanol and water have an azeotropic composition of C 2 H 5
Taking advantage of having OH / H 2 O (molar ratio) = 89.5 / 10.5,
Water can be removed by distilling with a large excess of ethanol.
The ethyl hemiacetal compound (hereinafter, abbreviated as TFA-EtOH) can be easily produced. This TFA-EtOH
Is azeotropic with ethanol at a boiling point of 103 ° C and has an azeotropic composition TFA-EtOH /
It is known that EtOH (molar ratio) = 82/12 is obtained as a fraction. [Chemische Berichte 106.2967 (19
73)] However, this method not only requires a large excess of ethanol, but also requires a great deal of cost for the dehydration equipment for ethanol after the treatment.
[課題を解決するための手段] 本発明者らは、かかる問題点を解決すべく鋭意検討した
結果、本発明に到達した。[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.
すなわち、本発明は、トリフルオロアセトアルデヒドの
水和物とメタノール,エタノール,プロパノールのうち
少なくとも1種類のアルコールを反応させる過程で、塩
化カルシウムを添加することを特徴とするヘミアセター
ル化合物の製造方法、およびさらにこの反応により生じ
る有機物層をゼオライトと接触させることを特徴とする
ヘミアセタール化合物の製造方法である。That is, the present invention provides a method for producing a hemiacetal compound, which comprises adding calcium chloride in the process of reacting a hydrate of trifluoroacetaldehyde with at least one alcohol selected from methanol, ethanol and propanol, and Further, it is a method for producing a hemiacetal compound, which comprises contacting an organic material layer generated by this reaction with zeolite.
前述の反応に、塩化カルシウムを添加することにより平
衡反応を右方向にずらすのみならず、二層分離が可能と
なり、上層の有機物層に99モル%以上の回収収率で原料
を回収でき、回収有機層中のヘミアセタール化合物の選
択率は95モル%以上になる。さらに残りの約5モル%の
TFA-H2Oをヘミアセタール化するため、該有機物層をゼ
オライトと接触させることにより有機物層中のヘミアセ
タール化合物の選択率を99モル%以上まで上げることが
でき、全体としての収率も99モル%以上となる。In addition to shifting the equilibrium reaction to the right by adding calcium chloride to the above reaction, it is possible to separate into two layers, and the raw material can be recovered in the recovery yield of 99 mol% or more in the upper organic layer, The selectivity of the hemiacetal compound in the organic layer is 95 mol% or more. And the remaining about 5 mol%
In order to hemiacetalize TFA-H 2 O, the selectivity of the hemiacetal compound in the organic layer can be increased to 99 mol% or more by bringing the organic layer into contact with zeolite, and the overall yield is 99%. It becomes more than mol%.
ここで、アルコールはTFAの水和物に対し、1.0〜2.5倍
当量、好ましくは1.0〜1.5倍当量加える。1.0倍当量よ
り少ないと当然目的生成物の収率が低く、2.5倍当量よ
り多いと効果は全く変わらないが経済的に不利となる。Here, the alcohol is added in an amount of 1.0 to 2.5 equivalents, preferably 1.0 to 1.5 equivalents, relative to the hydrate of TFA. If it is less than 1.0 times equivalent, the yield of the desired product is naturally low, and if it is more than 2.5 times equivalent, the effect is not changed but it is economically disadvantageous.
塩化カルシウムの添加量は、水和物中の水すなわちgem
−ジオール化合物中の水に対し、H2O/CaCl2のモル比で
2〜20、好ましくは3〜8が良い。20より多いと二層分
離が難しく、2より少ないと粘度が高くなり同様に層分
離が難しい。塩化カルシウムは、無水物に限らず二水
物,六水物等を使用しても良い。The amount of calcium chloride added depends on the water or gem in the hydrate.
The molar ratio of H 2 O / CaCl 2 to water in the diol compound is 2 to 20, preferably 3 to 8. When it is more than 20, it is difficult to separate the two layers, and when it is less than 2, the viscosity is high and similarly, the separation of the layers is difficult. As the calcium chloride, not only anhydrous but dihydrate, hexahydrate, etc. may be used.
反応温度は、室温より還流温度までの範囲、好ましくは
50℃〜還流温度の範囲である。反応温度が室温より低い
場合、粘度が高くなりすぎて層分離ができず、還流温度
より高いと蒸気圧が高くなりすぎ、設備等の面から考え
ても工業的に不利である。The reaction temperature is in the range of room temperature to reflux temperature, preferably
It is in the range of 50 ° C to the reflux temperature. When the reaction temperature is lower than room temperature, the viscosity becomes too high to separate the layers, and when the reaction temperature is higher than the reflux temperature, the vapor pressure becomes too high, which is industrially disadvantageous from the viewpoint of equipment.
ゼオライトは、有機物層に対し、重量で0.2倍当量以上
が好ましい。0.2倍等量より少ないと脱水効果が低下す
るため好ましくない。本発明で使用するゼオライトは、
特に限定されず脱水効果のあるものなら何でも使用する
ことができる。Zeolite is preferably 0.2 times equivalent or more by weight with respect to the organic layer. If the amount is less than 0.2 times the equivalent amount, the dehydration effect is reduced, which is not preferable. The zeolite used in the present invention is
Any material can be used without particular limitation as long as it has a dehydrating effect.
得られた化合物は安定であり、長期的な保存,運搬など
が容易に行え、必要によっては硫酸等との接触により脱
アルコールを行って元のアルデヒドとして使用すること
もでき、またそのまま中間体等として使用することもで
きる。The obtained compound is stable and can be easily stored and transported for a long period of time. If necessary, it can be dealcoholated by contact with sulfuric acid and used as the original aldehyde. Can also be used as
[実施例] 以下、本発明を実施例により詳細に説明するが、本発明
はこれらの実施例に限定されるものではない。[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
実施例1 攪拌機付の100ml三つ口フラスコに、トリフルオロアセ
トアルデヒド水和物(TFA-2.5H2O)を50g、エタノール
をTFAの1.2倍当量に当たる19.3g加え、無水塩化カルシ
ウムをTFA水和物中の水に対しH2O/CaCl2のモル比が6.0
になる量、すなわち16.2g添加して攪拌を行い、ジムロ
ートコンデンサーにて冷却させながら、油浴上で1時間
還流を行った。還流温度は95℃であった。Example 1 To a 100 ml three-necked flask equipped with a stirrer, 50 g of trifluoroacetaldehyde hydrate (TFA-2.5H 2 O) and 19.3 g of ethanol, which is 1.2 times equivalent of TFA, were added, and anhydrous calcium chloride was added to the TFA hydrate. The molar ratio of H 2 O / CaCl 2 to the water is 6.0.
Was added, that is, 16.2 g was added and stirred, and refluxed for 1 hour on an oil bath while cooling with a Dimroth condenser. The reflux temperature was 95 ° C.
攪拌を止め、内液温度が50℃以下に冷却された所で分液
ロートに移し、二層分離した各層を分取した結果、上層
の有機物は58.0g、下層は27.5gであった。When the stirring was stopped and the internal liquid temperature was cooled to 50 ° C or lower, the liquid was transferred to a separating funnel and the two layers separated were separated. As a result, the upper layer organic matter was 58.0 g and the lower layer was 27.5 g.
上層の有機物は、トリフルオロ酢酸を基準として19F-NM
Rで求めたところ、エチルヘミアセタール(TFA-EtOH)4
7.9g,gem−ジオール(TFA-H2O)1.8gでその他はエタ
ノールであった。ここでのTFA-EtOHの選択率は95.5モル
%で、原料の回収率は99.5%であり、TFA-EtOHの収率は
TFA基準で95.0%であった。The upper organic matter is 19 F-NM based on trifluoroacetic acid.
When calculated by R, ethyl hemiacetal (TFA-EtOH) 4
7.9 g, gem-diol (TFA-H 2 O) 1.8 g, and others were ethanol. The selectivity of TFA-EtOH here is 95.5 mol%, the recovery of raw materials is 99.5%, and the yield of TFA-EtOH is
It was 95.0% by TFA standard.
該有機物を、100ml二つ口フラスコに入れ、モレキュラ
シーブ3A(和光純薬製)10gを入れてマグネチックス
ターラーで4時間攪拌した結果、TFA-EtOHの選択率は9
9.4モル%まで上昇し、収率は99%であった。The organic matter was placed in a 100 ml two-necked flask, 10 g of molecular sieve 3A (manufactured by Wako Pure Chemical Industries) was placed therein, and the mixture was stirred with a magnetic stirrer for 4 hours. As a result, the selectivity of TFA-EtOH was 9
The yield increased to 9.4 mol% and the yield was 99%.
実施例2 実施例1においてアルコールをメタノールに代えて同様
の反応を行った。メタノールは13.5g添加し、還流温度
は96℃であった。Example 2 The same reaction was performed as in Example 1 except that alcohol was replaced with methanol. 13.5 g of methanol was added, and the reflux temperature was 96 ° C.
二層分離後の上層の有機物はメチルヘミアセタール(TF
A-MeOH)43.6g,gem−ジオール(TFA-H2O)1.1gで、T
FA-MeOHの選択率は97.3モル%であった。一方、原料の
回収率は99.3%であり、TFA-MeOHの収率はTFA基準で96.
6%であった。After separation of the two layers, the organic material in the upper layer is methyl hemiacetal (TF
A-MeOH) 43.6 g, gem-diol (TFA-H 2 O) 1.1 g, T
The FA-MeOH selectivity was 97.3 mol%. On the other hand, the raw material recovery rate is 99.3%, and the yield of TFA-MeOH is 96 on a TFA basis.
It was 6%.
さらに、モレキュラシーブ3Aで処理した結果、TFA-Me
OHの選択率は99.7モル%まで上昇した。Furthermore, as a result of treatment with Molecular Sieve 3A, TFA-Me
The OH selectivity increased to 99.7 mol%.
比較例1 実施例1において無水塩化カルシウムを添加せずに同様
に行ったところ、均一層中のTFA-MtOHは33.8g,TFA-H2
Oは13.4gで、TFA-EtOHの選択率は67.0モル%であっ
た。Comparative Example 1 When the same procedure as in Example 1 was carried out without adding anhydrous calcium chloride, TFA-MtOH in the uniform layer was 33.8 g, and TFA-H 2
O was 13.4 g, and the selectivity of TFA-EtOH was 67.0 mol%.
比較例2 実施例2において無水塩化カルシウムを添加せずに同様
に行ったところ、均一層中のTFA-MeOHは33.2g,TFA-H2
Oは10.8gで、TFA-MeOHの選択率は73.5モル%であっ
た。Comparative Example 2 When the same procedure as in Example 2 was carried out without adding anhydrous calcium chloride, 33.2 g of TFA-MeOH and TFA-H 2 in the uniform layer were obtained.
O was 10.8 g and the selectivity of TFA-MeOH was 73.5 mol%.
[発明の効果] 本発明の製造方法によれば、塩化カルシウムを反応過程
で添加することによって、二層分離された有機層中に高
収率,高選択率でヘミアセタール化合物を得ることがで
き、該有機物層をゼオライトと接触させることでヘミア
セタール化合物の選択率をさらに向上させることができ
るものである。[Effect of the Invention] According to the production method of the present invention, by adding calcium chloride in the reaction process, a hemiacetal compound can be obtained in a high yield and a high selectivity in an organic layer separated into two layers. By contacting the organic layer with zeolite, the selectivity of the hemiacetal compound can be further improved.
Claims (2)
メタノール,エタノール,プロパノールのうち少なくと
も1種類のアルコールを反応させる過程で、塩化カルシ
ウムを添加することを特徴とするヘミアセタール化合物
の製造方法。1. A process for producing a hemiacetal compound, which comprises adding calcium chloride in the process of reacting a hydrate of trifluoroacetaldehyde with at least one alcohol selected from methanol, ethanol and propanol.
さらにゼオライトと接触させることを特徴とするヘミア
セタール化合物の製造方法。2. A method for producing a hemiacetal compound, which further comprises contacting the organic layer formed by the reaction of claim 1 with zeolite.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29432988A JPH0635412B2 (en) | 1988-11-21 | 1988-11-21 | Method for producing hemiacetal compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29432988A JPH0635412B2 (en) | 1988-11-21 | 1988-11-21 | Method for producing hemiacetal compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02138145A JPH02138145A (en) | 1990-05-28 |
JPH0635412B2 true JPH0635412B2 (en) | 1994-05-11 |
Family
ID=17806291
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29432988A Expired - Lifetime JPH0635412B2 (en) | 1988-11-21 | 1988-11-21 | Method for producing hemiacetal compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0635412B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4891591B2 (en) * | 2005-10-25 | 2012-03-07 | 東ソ−・エフテック株式会社 | Method for recovering trifluoroacetaldehyde hemiacetal |
JP2013159606A (en) * | 2012-02-09 | 2013-08-19 | Polyplastics Co | Method for producing formaldehyde gas and apparatus for producing formaldehyde gas |
-
1988
- 1988-11-21 JP JP29432988A patent/JPH0635412B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH02138145A (en) | 1990-05-28 |
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