JP4056105B2 - Storage method for halogen-substituted acetal monomers - Google Patents
Storage method for halogen-substituted acetal monomers Download PDFInfo
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- JP4056105B2 JP4056105B2 JP14828697A JP14828697A JP4056105B2 JP 4056105 B2 JP4056105 B2 JP 4056105B2 JP 14828697 A JP14828697 A JP 14828697A JP 14828697 A JP14828697 A JP 14828697A JP 4056105 B2 JP4056105 B2 JP 4056105B2
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- halogen
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- acetal
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Description
【0001】
【発明の属する技術分野】
本発明は、ハロゲン置換アセタ−ルモノマ−の貯蔵方法に関する。ハロゲン置換アセタ−ルモノマ−は、医薬、農薬などの製造中間体として有用な化合物である。
【0002】
【従来の技術】
アセタ−ル化合物は、酸触媒および強塩基存在下で容易に加水分解を起こし、脱アセタ−ル化することが知られている。さらに、一般式(I)で表されるハロゲン置換アセタ−ルモノマ−はその構造上、脱ハロゲン化水素が起こりやすく、そのため一般のアセタ−ル類よりも分解しやすい特徴を有する。
【0003】
ハロゲン置換アセタ−ルモノマ−を安定に長期保存させる方法は、特公昭50−38105を除き知られていない。そこに記載されているアセタ−ルモノマ−を安定化させる方法は、炭酸カリウム、ホウ酸ナトリウムまたは第1リン酸カリウムを共存させるものである。しかし、ここで用いる塩基はいずれも固体塩基であり、アセタ−ル類に一般的に溶解せず不均一となるため、効果を持続させるためには系を均一にさせる等の工夫が必要である。
【0004】
アセタ−ル化合物の加水分解は、保存温度が高いほど分解しやすく、含水率が高いほど分解しやすい。従って、水分を含むアセタ−ルモノマ−の夏場のタンクでの保存を想定すると、高温下においても安定にアセタ−ルモノマ−を保存できる方法の開発が望まれる。
【0005】
【発明が解決しようとする課題】
特公昭50−38105に記載されている固体塩基はアセタ−ルモノマ−には溶解しないため、系は不均一となる。そのため長期保存には、無機塩基とアセタ−ルモノマ−を接触させる工夫が必要であった。さらに、水分を含むアセタ−ルモノマ−の夏場のタンクでの保存を想定すると、高温下においてもアセタ−ルモノマ−を安定に保存可能な技術を確立する必要性があった。本発明は、無機塩基ではなく有機塩基を用いる事により先に示した課題を克服し、高温下においてもアセタ−ルモノマ−を安定に貯蔵する方法を提供するものである。
【0006】
【課題を解決するための手段】
本発明は、含水率が0.001ないし10重量パ−セントであるアセタ−ルモノマ−100重量部に対し、有機塩基0.1ないし10重量部を共存させ、一般式(I)で表される化合物を安定に貯蔵する方法を提供するものである。
【0007】
【発明の実施形態】
本発明の対象とするハロゲン置換アセタ−ルモノマ−は、
一般式(I)
【化2】
で表すことができる。但し、式中、R1は直鎖低級アルキル基、R2、R3、R4、R5は水素原子、直鎖低級アルキル基、分枝低級アルキル基、およびアリ−ル基を意味し、Xはハロゲン原子を意味し具体的には塩素原子、臭素原子、ヨウ素原子を意味する。
【0008】
例えば、3−クロロプロピオンアルデヒド ジメチルアセタ−ル、3−クロロプロピオンアルデヒド ジエチルアセタ−ル、3−ブロモプロピオンアルデヒドジプロピルアセタ−ル、3−ヨ−ドプロピオンアルデヒド ジメチルアセタ−ル、3−クロロブチロアルデヒド ジエチルアセタ−ル、3−クロロイソヴァレロアルデヒド ジメチルアセタ−ル、3−クロロシンナムアルデヒド ジエチルアセタ−ル、3−ブロモ−2−メチルプロピオンアルデヒド ジメチルアセタ−ル、3−クロロ−2−メチルヴァレロアルデヒド ジエチルアセタ−ル、3−クロロ−2−メチルシンナムアルデヒド ジメチルアセタ−ル、2−クロロエチルメチル ケトン ジエチルアセタ−ル、2−クロロ−2−フェニルエチル メチル ケトン ジメチルアセタ−ル等を挙げることができる。
【0009】
本発明の特徴をなす安定化剤は有機塩基であり、なかでも有機アミンが好ましい物質であり、特に3級アミンおよびピリジン骨格を有するアミンが効果的で望ましい。
【0010】
例えば、メチルアミン、エチルアミン、イソプロピルアミン、ブチルアミン、ジメチルアミン、ジエチルアミン、ジイソプロピルアミン、トリメチルアミン、トリエチルアミン、トリブチルアミン、N−メチルピペリジン、N−メチルピロリジン、ピリジン、メチルピリジン、ジメチルピリジン、トリメチルピリジン等を挙げることができる。
【0011】
本発明を実施するとき、安定化剤として有機塩基を添加する。有機塩基の役割は、ハロゲン置換アセタ−ルモノマ−が分解する際に発生するハロゲン化水素を補足することにある。このことから、有機塩基の添加量は多いほど望ましいといえる。有機塩基の添加量は、一般式(I)で表されるハロゲン置換アセタ−ルモノマ−100重量部に対し、有機塩基0.1ないし10重量部、好ましくは0.5ないし5重量部を共存させることが望ましい。
【0012】
本発明を実施するとき、含水量と添加する有機塩基の量によりハロゲン置換アセタ−ルモノマ−の分解速度が異なる。含水量が多い場合は、有機塩基の添加量を多くするほうがハロゲン置換アセタ−ルモノマ−の分解を抑制できるので望ましい。逆に、含水量が少ない場合は、有機塩基の添加量は少なくても良い。すなわち、含水量が0.1重量部ないし10重量部のときは、有機塩基の添加量は2重量部ないし10重量部が望ましい。含水量が0.001重量部ないし0.1重量部のときは、有機塩基の添加量は0.1重量部ないし2重量部で保存効果を現す。
【0013】
【実施例】
(実施例1) 密封度の高いガラス容器に、所定量の水を含んだ3−クロロプロピオンアルデヒド ジエチルアセタ−ル(純度98.61%)15.0gにトリエチルアミンを所定量加え密封した後、所定温度にて所定時間保存後、アセタ−ルの含量をGLC内部標準法にて分析した。分析結果を表1に示す。尚、表1中のアセタ−ル含量の保持率とは、実験開始前のアセタ−ルモノマ−の正味の量を100としたときのアセタ−ルモノマ−の含量変化の割合を示す。
【0014】
【表1】
(実施例2) 密封度の高いガラス容器に、含水量0.05%の3−ブロモ−2−メチルプロピオンアルデヒド ジメチルアセタ−ル(純度97.39%)15.0gに、トリブチルアミンを所定量加え密封した後、所定温度にて所定時間保存後、アセタ−ルの含量をGLC内部標準法にて分析した。分析結果を表2に示す。尚、表2中のアセタ−ル含量の保持率とは、実験開始前のアセタ−ルモノマ−の正味の量を100としたときのアセタ−ルモノマ−の含量変化の割合を示す。
【0015】
【表2】
(実施例3) 密封度の高いガラス容器に、含水量0.02%の3−クロロ−2−メチルヴァレロアルデヒド ジエチルアセタ−ル(純度98.26%)15.0gに、N−メチルピペリジンを所定量加え密封した後、所定温度にて所定時間保存後、アセタ−ルの含量をGLC内部標準法にて分析した。分析結果を表3に示す。尚、表3中のアセタ−ル含量の保持率とは、実験開始前のアセタ−ルモノマ−の正味の量を100としたときのアセタ−ルモノマ−の含量変化の割合を示す。
【0016】
【表3】
【0017】
【発明の効果】
一般式(I)で表され、且つ含水率が0.001ないし10重量パ−セントであるアセタ−ルモノマ−100重量部に対し、有機塩基0.1ないし10重量部を共存させることにより、一般式(I)で表されるハロゲン置換アセタ−ルモノマ−を安定に長期間貯蔵することを可能にする。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for storing halogen-substituted acetal monomers. Halogen-substituted acetyl monomer is a useful compound as an intermediate for producing pharmaceuticals, agricultural chemicals and the like.
[0002]
[Prior art]
Acetal compounds are known to easily hydrolyze and deacetate in the presence of acid catalysts and strong bases. Furthermore, the halogen-substituted acetyl monomer represented by the general formula (I) is characterized in that dehydrohalogenation is likely to occur due to its structure, and therefore has a characteristic that it is more easily decomposed than general acetals.
[0003]
A method for stably storing a halogen-substituted acetyl monomer for a long period of time is not known except for Japanese Patent Publication No. 50-38105. The method for stabilizing the acetyl monomer described therein coexists potassium carbonate, sodium borate or primary potassium phosphate. However, all the bases used here are solid bases and generally do not dissolve in acetals and become non-uniform. Therefore, in order to maintain the effect, it is necessary to make a system uniform. .
[0004]
The hydrolysis of the acetal compound is easier to decompose as the storage temperature is higher, and it is easier to decompose as the moisture content is higher. Accordingly, assuming storage of moisture-containing acetyl monomer in a summer tank, it is desired to develop a method that can stably store acetyl monomer even at high temperatures.
[0005]
[Problems to be solved by the invention]
Since the solid base described in JP-B-50-38105 does not dissolve in the acetal monomer, the system becomes heterogeneous. Therefore, a device for bringing an inorganic base and an acetal monomer into contact with each other is necessary for long-term storage. Further, assuming that the acetal monomer containing moisture is stored in a tank in summer, there is a need to establish a technique that can stably store the acetal monomer even at high temperatures. The present invention overcomes the above-mentioned problems by using an organic base instead of an inorganic base, and provides a method for stably storing an acetal monomer even at high temperatures.
[0006]
[Means for Solving the Problems]
In the present invention, 0.1 to 10 parts by weight of an organic base coexists with 100 parts by weight of an acetal monomer having a water content of 0.001 to 10% by weight, and is represented by the general formula (I). A method of stably storing a compound is provided.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The halogen-substituted acetyl monomer that is the subject of the present invention is:
Formula (I)
[Chemical 2]
Can be expressed as In the formula, R1 represents a linear lower alkyl group, R2, R3, R 4 and R 5 represent a hydrogen atom, a linear lower alkyl group, a branched lower alkyl group, and an aryl group, and X represents a halogen atom. It means an atom, specifically a chlorine atom, a bromine atom, or an iodine atom.
[0008]
For example, 3-chloropropionaldehyde dimethyl acetal, 3-chloropropionaldehyde diethyl acetal, 3-bromopropionaldehyde dipropyl acetal, 3-iodopropionaldehyde dimethyl acetal, 3-chlorobutyraldehyde diethyl acetal -Chloro, 3-chloroisovaleraldehyde dimethyl acetal, 3-chlorocinnamaldehyde diethyl acetal, 3-bromo-2-methylpropionaldehyde dimethyl acetal, 3-chloro-2-methylvaleraldehyde diethyl acetal, Examples include 3-chloro-2-methylcinnamaldehyde dimethyl acetal, 2-chloroethyl methyl ketone diethyl acetal, 2-chloro-2-phenylethyl methyl ketone dimethyl acetal, etc. Door can be.
[0009]
Stabilizers that characterize the present invention are organic bases, among which organic amines are preferred materials, with tertiary amines and amines having a pyridine skeleton being particularly effective and desirable.
[0010]
For example, methylamine, ethylamine, isopropylamine, butylamine, dimethylamine, diethylamine, diisopropylamine, trimethylamine, triethylamine, tributylamine, N-methylpiperidine, N-methylpyrrolidine, pyridine, methylpyridine, dimethylpyridine, trimethylpyridine and the like. be able to.
[0011]
When practicing the present invention, an organic base is added as a stabilizer. The role of the organic base is to supplement the hydrogen halide generated when the halogen-substituted acetyl monomer is decomposed. From this, it can be said that the larger the amount of organic base added, the better. The organic base is added in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the halogen-substituted acetyl monomer represented by formula (I). It is desirable.
[0012]
When practicing the present invention, the decomposition rate of the halogen-substituted acetyl monomer varies depending on the water content and the amount of organic base added. When the water content is high, it is desirable to increase the amount of the organic base added because decomposition of the halogen-substituted acetyl monomer can be suppressed. Conversely, when the water content is low, the amount of organic base added may be small. That is, when the water content is 0.1 to 10 parts by weight, the addition amount of the organic base is preferably 2 to 10 parts by weight. When the water content is 0.001 to 0.1 parts by weight, the storage effect is exhibited when the addition amount of the organic base is 0.1 to 2 parts by weight.
[0013]
【Example】
(Example 1) A glass container having a high degree of sealing was sealed by adding a predetermined amount of triethylamine to 15.0 g of 3-chloropropionaldehyde diethylacetal (purity 98.61%) containing a predetermined amount of water, and then a predetermined temperature. After storage for a predetermined time, the content of acetal was analyzed by the GLC internal standard method. The analysis results are shown in Table 1. The retention rate of the acetyl monomer content in Table 1 indicates the rate of change in the acetyl monomer content when the net amount of the acetyl monomer before the start of the experiment is taken as 100.
[0014]
[Table 1]
(Example 2) A predetermined amount of tributylamine was added to 15.0 g of 3-bromo-2-methylpropionaldehyde dimethylacetal (purity 97.39%) having a water content of 0.05% in a highly sealed glass container. After sealing, the acetal content was analyzed by the GLC internal standard method after storing at a predetermined temperature for a predetermined time. The analysis results are shown in Table 2. The retention rate of the acetyl monomer content in Table 2 indicates the rate of change in the acetyl monomer content when the net amount of acetyl monomer before the start of the experiment is taken as 100.
[0015]
[Table 2]
(Example 3) N-methylpiperidine was added to 15.0 g of 3-chloro-2-methylvaleraldehyde diethylacetal (purity 98.26%) having a water content of 0.02% in a highly sealed glass container. After a predetermined amount was added and sealed, it was stored at a predetermined temperature for a predetermined time, and then the acetal content was analyzed by the GLC internal standard method. The analysis results are shown in Table 3. The retention rate of the acetyl monomer content in Table 3 indicates the rate of change in the acetyl monomer content when the net amount of acetyl monomer before the start of the experiment is taken as 100.
[0016]
[Table 3]
[0017]
【The invention's effect】
By adding 0.1 to 10 parts by weight of an organic base to 100 parts by weight of an acetyl monomer having a general formula (I) and a water content of 0.001 to 10 parts by weight, This makes it possible to stably store the halogen-substituted acetyl monomer represented by the formula (I) for a long period of time.
Claims (1)
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JP14828697A JP4056105B2 (en) | 1997-06-05 | 1997-06-05 | Storage method for halogen-substituted acetal monomers |
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JP14828697A JP4056105B2 (en) | 1997-06-05 | 1997-06-05 | Storage method for halogen-substituted acetal monomers |
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JPH10338655A JPH10338655A (en) | 1998-12-22 |
JP4056105B2 true JP4056105B2 (en) | 2008-03-05 |
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JP6213417B2 (en) | 2014-07-30 | 2017-10-18 | セントラル硝子株式会社 | Method for improving storage stability of 2,2-difluoroacetaldehyde |
JP6195028B1 (en) * | 2017-02-02 | 2017-09-13 | セントラル硝子株式会社 | Method for preserving α, α-difluoroacetaldehyde alkyl hemiacetal |
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