JPS6024777B2 - Method for producing alkaline earth metal salt of aliphatic β-keto compound - Google Patents
Method for producing alkaline earth metal salt of aliphatic β-keto compoundInfo
- Publication number
- JPS6024777B2 JPS6024777B2 JP5469176A JP5469176A JPS6024777B2 JP S6024777 B2 JPS6024777 B2 JP S6024777B2 JP 5469176 A JP5469176 A JP 5469176A JP 5469176 A JP5469176 A JP 5469176A JP S6024777 B2 JPS6024777 B2 JP S6024777B2
- Authority
- JP
- Japan
- Prior art keywords
- aliphatic
- alkaline earth
- earth metal
- hydroxide
- reaction
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は脂肪族8ーケト化合物のアルカリ士類金属塩の
製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for preparing alkali metal salts of aliphatic 8-keto compounds.
更に詳しくは本発明は、脂肪族6−ケトェステル類もし
くはB−ジケトン類を無溶媒で水酸化アルカリ士類金属
と処理して、対応するアルカリ士類金属塩類を得ること
を特徴とする脂肪族8−ケト化合物のアルカリ士類金属
塩の製法に関する。More specifically, the present invention is characterized in that aliphatic 6-ketesters or B-diketones are treated with an alkali metal hydroxide without a solvent to obtain the corresponding alkali metal salts. - A method for producing an alkali metal salt of a keto compound.
従来より脂肪族8ーケト化合物のアルカリ士類金属塩、
例えばアセト酢酸エチルェステルやアセチルアセトンの
カルシウム塩は塩ビを成型する際に無毒性安定剤として
広く用いられているものである。それらの合成法として
は種々の方法があるが、たとえばアセト酢酸エチルのカ
ルシウム塩の合成法としては【1’無水エタノール中で
金属カルシウムと処理する方法〔Zh.0bscheK
him・42403(1972)〕、‘2}無水ベンゼ
ン中で炭化カルシウムまたは酸化カルシウムと処埋する
方法(J.Chem.SMへ1951、2505)があ
り、またアセチルアセトンのアルカリ士類金属塩の合成
法としては‘3}アンモニアを用いてケチミンを形成後
、金属塩と処理して置換する方法(蛇r.1、0390
56)、■水性溶媒中で金属水酸化物と処理する方法〔
Compt.Rendへ 157、50(1913)〕
などが挙げられる。Conventionally, alkali metal salts of aliphatic 8-keto compounds,
For example, acetoacetic acid ethyl ester and calcium salts of acetylacetone are widely used as non-toxic stabilizers when molding PVC. There are various methods for synthesizing them; for example, a method for synthesizing calcium salts of ethyl acetoacetate is [method of treating with metallic calcium in 1' absolute ethanol [Zh. 0bscheK
Him 42403 (1972)], '2} There is a method of processing with calcium carbide or calcium oxide in anhydrous benzene (J. Chem. SM 1951, 2505), and a method of synthesizing alkali metal salts of acetylacetone. '3} A method in which ketimine is formed using ammonia and then treated with a metal salt to replace it (Snake r.1, 0390
56), ■Method of treatment with metal hydroxide in an aqueous solvent [
Compt. To Rend 157, 50 (1913)]
Examples include.
しかしこれらの方法はそれぞれに欠点があり、工業的規
模で生産するには不利益点が多かった。However, each of these methods has its own drawbacks, and there are many disadvantages when producing on an industrial scale.
たとえば‘1)の方法では高価な金属カルシウムを用い
ているのでコスト面で問題があり、‘2)の方法では炭
化カルシウムを用いる場合には高純度な炭化カルシウム
が得がたく、かつ高い硬度を有するため粉末として添加
いこくいという欠点があり、また酸化カルシウムを用い
る方法は唯一の工業化可能な方法であるが、反応の進行
が非常に遅く、進行に伴ってゲル化し、かつ黄色に着色
するという欠点があった。一方、‘2}の方法を改良し
てベンゼン中で水酸化カルシウムと処理すると反応は容
易に進行するようになるが反応液全体がゲル化し反応終
了後ベンゼンを濃縮すると粘鋼な成績体となり結晶化い
こくく、その上着色された生成物しか得られなかった。
一方、近年では公害面の規制が厳しくなり、水質汚染の
原因となりやすい有機溶媒の使用は必要最小限にとどめ
ることが望ましく、前記化合物の製造においても実質的
に無溶媒の条件下で製造することが望まれていた。この
ような事情のため、本発明の発明者は脂肪族8ーケトェ
ステル類および脂肪族8ージケトン類のアルカリ士類金
属塩を実質的に無溶媒下で安価な原料を用いた簡便な方
法で高純度の生成物を得ることを目的として研究を重ね
た結果、本発明に到達した。かくして、この発明による
8−ケト化合物のアルカリ士類金属塩の製法は脂肪族8
−ケトェステル類および脂肪族8−ジケトン類に無溶媒
下で水酸化アルカリ士類金属を少量ずつ加えて反応を行
なうことよりなる。For example, method '1) uses expensive metallic calcium, which poses a cost problem, and method '2) uses calcium carbide, which makes it difficult to obtain high-purity calcium carbide and requires high hardness. However, the method using calcium oxide is the only industrially viable method, but the reaction progresses very slowly, gels as it progresses, and is colored yellow. There were drawbacks. On the other hand, if the method '2} is improved and treated with calcium hydroxide in benzene, the reaction will proceed easily, but the entire reaction solution will turn into a gel, and if the benzene is concentrated after the reaction, it will become a viscous product and crystallize. Only a colored product was obtained.
On the other hand, in recent years, regulations regarding pollution have become stricter, and it is desirable to keep the use of organic solvents, which tend to cause water pollution, to the minimum necessary, and it is also desirable to manufacture the above compounds under substantially solvent-free conditions. was desired. Under these circumstances, the inventor of the present invention has developed highly pure alkali metal salts of aliphatic 8-ketesters and aliphatic 8-diketones by a simple method using inexpensive raw materials in a substantially solvent-free environment. As a result of repeated research aimed at obtaining a product, the present invention was achieved. Thus, the method for preparing alkali metal salts of 8-keto compounds according to the present invention provides a method for preparing alkali metal salts of 8-keto compounds.
- The reaction is carried out by adding alkali metal hydroxide little by little to ketoesters and aliphatic 8-diketones in the absence of a solvent.
この方法によると無溶媒下を極めて容易に反応が進行し
、しかも加水分解を誘発するほどの発熱もなく高収率で
目的物を得ることができる。また反応が実質的に終了後
、水またはメタノールを添加すれば、目的物の採取が容
易になるなどの利点がある。この発明に使用される脂肪
族8ーケトェステル類および脂肪族8−ジケトン類は、
次の一般式【1,:R,COCH2COR2
(1)(式中R,はアルキル基を示し、R2はア
ルキル基またはアルキルオキシ基を示す。According to this method, the reaction proceeds extremely easily in the absence of a solvent, and the desired product can be obtained in high yield without generating heat that would induce hydrolysis. Further, if water or methanol is added after the reaction is substantially completed, there is an advantage that the target product can be easily collected. The aliphatic 8-ketesters and aliphatic 8-diketones used in this invention are:
The following general formula [1,:R, COCH2COR2
(1) (In the formula, R represents an alkyl group, and R2 represents an alkyl group or an alkyloxy group.
)で表わされる。).
本発明に使用するのに特に適切な化合物はR,およびR
2が炭素数1〜3の低級アルキル基あるいは低級アルキ
ルオキシ基であるものである。このうち特にアセト酢酸
エチル、アセト酢酸メチルおよびアセチルアセトンが好
ましい。また水酸化アルカリ士類金属としては水酸化カ
ルシウム、水酸化マグネシウムおよび水酸化バリウムが
含まれる。脂肪族Pーケト化合物と水酸化アルカリ士類
金属との使用割合は1:1であることが好ましい。反応
は多少発熱的であるため、脂肪族8−ケト化合物に常温
で水酸化アルカリ士類金属を少量ずつ加え、適宜発熱坂
吏応を保ちながら反応を行なうのが望ましい。Particularly suitable compounds for use in the present invention are R, and R
2 is a lower alkyl group or a lower alkyloxy group having 1 to 3 carbon atoms. Among these, ethyl acetoacetate, methyl acetoacetate and acetylacetone are particularly preferred. Further, the alkali metal hydroxides include calcium hydroxide, magnesium hydroxide, and barium hydroxide. The ratio of the aliphatic P-keto compound to the alkali metal hydroxide is preferably 1:1. Since the reaction is somewhat exothermic, it is desirable to add the alkali metal hydroxide little by little to the aliphatic 8-keto compound at room temperature and carry out the reaction while appropriately maintaining the exothermic slope.
反応終了後は特別な処理をする必要もなく、高収率で純
度の高い目的物を得ることができる。またより純度の高
い生成物を得たい場合は水またはメタノールを加えるこ
とにより少量残った未反応物について反応を完結するこ
とができ、また目的物の採取も容易にすることができる
。この場合、加える水またはメタノールの量は脂肪族8
−ケト化合物の使用重量の2倍までであることが好まし
い。かくして得られた脂肪族8−ケト化合物のアルカリ
士類金属塩は着色もなく非常に高秦制度のものである。
次に本発明を実施例によって説明する。After the reaction is completed, there is no need for any special treatment, and the target product can be obtained in high yield and with high purity. Furthermore, if it is desired to obtain a product with higher purity, the reaction can be completed for a small amount of unreacted material by adding water or methanol, and collection of the target product can also be facilitated. In this case, the amount of water or methanol added is
- Preferably up to twice the weight of the keto compound used. The alkali metal salt of the aliphatic 8-keto compound thus obtained has no coloration and is of very high quality.
Next, the present invention will be explained by examples.
実施例 1
アセト酢酸エチルカルシウム塩
3そのすりつぶし磯にアセト酢酸エチル390夕と水酸
化カルシウム20夕を加え蝿梓を開始する。Example 1 Ethyl acetoacetate calcium salt 3 390 ml of ethyl acetoacetate and 20 ml of calcium hydroxide are added to the ground mixture to start the process.
約1分後に反応が始まり、続いて水酸化カルシウム10
タづっを2〜3分毎に加えて行くと反応液はゲル化して
来る。更に加えつづけ約70夕を加えた頃最高温度(約
40℃)に達する。全量が111のこなるまで水酸化カ
ルシウムを加え、40〜50分反応後7び0にて3時間
乾燥すると淡桃色のァセト酢酸エチルカルシウム塩44
4夕を得る。(収率:99.3%)mP21ぴ○(分解
)
実施例 2
アセト酢酸メチルカルシウム塩
3そのすりつぶし機にアセト酢酸メチル私8夕と水酸化
カルシウム20夕を加え実施例1と同様に反応させると
白色のアセト酢酸メチルカルシウム塩369夕を得る。The reaction begins after about 1 minute, followed by calcium hydroxide 10
When adding Tazu every 2 to 3 minutes, the reaction solution becomes a gel. Further addition was continued, reaching the maximum temperature (approximately 40°C) after approximately 70 evenings. Add calcium hydroxide until the total amount becomes 111, react for 40 to 50 minutes, and then dry at 7 and 0 for 3 hours to obtain pale pink ethyl acetoacetate calcium salt 44.
Get 4 evenings. (Yield: 99.3%) mP21pi○ (decomposition) Example 2 Methyl acetoacetate calcium salt 3 Add 80% of methyl acetoacetate and 20% of calcium hydroxide to the grinder and react in the same manner as in Example 1. A white methylcalcium acetoacetate salt 369 was obtained.
(収率:91.1%)mP22で○(分解)
実施例 3
アセチルアセトンカルシウム塩
3そのすりつぶし機アセチルアセトン300夕と水酸化
カルシウム209を加え実施例1と同様に反応させると
白色のアセチルァセトンカルシゥム塩の粉末結晶312
夕を得る。(Yield: 91.1%) ○ (decomposition) at mP22 Example 3 Acetylacetone calcium salt 3 Grinding machine 300 g of acetylacetone and 209 g of calcium hydroxide are added and reacted in the same manner as in Example 1 to produce white acetylacetone calcium. Salt powder crystal 312
Get the evening.
(収率:87.2%)mP26.8qo(分解)実施例
4
アセチルアセトンマグネシウム塩
3そのすりつぶし機にアセチルアセトン300夕と水酸
化マグネシウム10夕を加え縄梓を開始する。(Yield: 87.2%) mP26.8qo (decomposition) Example 4 Magnesium acetylacetone salt 3 Add 300 g of acetylacetone and 10 g of magnesium hydroxide to the grinder and start grinding.
約1分後に反応が始まり続いて水酸化マグネシウム5タ
づつを2〜3分毎に加えて行くと反応液はゲル化して釆
る。更に加えつづけ約60夕を加えた頃最高温度(7ぴ
○)に達する。全量87.6夕になるまで水酸化マグネ
シウムを加え約1時間反応後、8び0にて3時間乾燥す
ると白色のアセチルアセトンマグネシウム塩の粉末結晶
309夕を得る。(収率:滋.7%)mP154℃(分
解)
実施例 5
アセト酢酸エチルマグネシウム塩
3そのすりつぶし機にアセト酢酸エチル390夕と水酸
化マグネシウム102を加え実施例4と同様に反応する
。The reaction starts after about 1 minute, and then 5 tons of magnesium hydroxide is added every 2 to 3 minutes, and the reaction solution turns into a gel and boils. Further addition was continued until the maximum temperature (7 pi○) was reached after about 60 days. Magnesium hydroxide was added until the total amount reached 87.6 mm, and the mixture was reacted for about 1 hour, and then dried at 8°C for 3 hours to obtain 309 mm of white acetylacetone magnesium salt powder crystals. (Yield: 0.7%) mP 154°C (decomposition) Example 5 Ethyl acetoacetate magnesium salt 3 To the grinder were added 390 g of ethyl acetoacetate and 102 g of magnesium hydroxide, and the reaction was carried out in the same manner as in Example 4.
(最高温度70℃)80qoにて乾燥すると白色のアセ
ト酢酸エチルマグネシウム塩の粉末結晶367夕を得る
。(収率:865%)mP244qo(分解)
実施例 6
アセト酢酸エチルカルシウム塩
実施例1の方法に準じて反応を行ない水酸化カルシウム
全量を加え約3び分反応後、反応を完結するためメチル
アルコール220夕を加えなお蝿梓を10〜20分持続
し、その後吸引ろ過した後結晶を70℃にて乾燥すると
アセト酢酸エチルカルシウム塩396夕を得る。Drying at 80 quarts (maximum temperature 70° C.) yields 367 white powder crystals of ethylmagnesium acetoacetate. (Yield: 865%) mP244qo (decomposition) Example 6 Ethyl calcium acetoacetate The reaction was carried out according to the method of Example 1, and the total amount of calcium hydroxide was added, and after about 3 minutes of reaction, methyl alcohol was added to complete the reaction. Add 220 ml of ethyl acetate and continue to stir for 10 to 20 minutes, then filter under suction and dry the crystals at 70°C to obtain ethyl acetoacetate calcium salt 396 ml.
(収率:柵.6%)mP220qo(分解)
実施例 7
アセチルアセトンカルシウム塩
実施例3の方法に準じて反応を行ない水酸化カルシウム
全量を加え、約30分反応後反応を完結するため蒸留水
300夕を加えなお縄拝を10〜2び分持続し、その後
吸引ろ過した後、結晶を70qoにて乾燥するとアセチ
ルアセトンカルシウム塩の粉末結晶304.4夕を得る
。(Yield: .6%) mP220qo (decomposition) Example 7 Acetylacetone calcium salt The reaction was carried out according to the method of Example 3, the total amount of calcium hydroxide was added, and after about 30 minutes of reaction, 300 g of distilled water was added to complete the reaction. After adding water and continuing the stirring for 10 to 2 minutes, the crystals are dried at 70 qo after suction filtration to obtain 304.4 qo powder crystals of acetylacetone calcium salt.
Claims (1)
を無溶媒で水酸化アルカリ土類金属と処埋して、対応す
るアルカリ土類金属塩類を得ることを特徴とする脂肪族
β−ケト化合物のアルカリ土類金属塩の製法。 2 脂肪族β−ケトエステル類がアセト酢酸エチルまた
はアセト酢酸メチルである特許請求の範囲第1項記載の
方法。 3 脂肪族β−ジケトン類がアセチルアセトンである特
許請求の範囲第1項記載の方法。 4 水酸化アルカリ土類金属が水酸化カルシウム、水酸
化マグネシウムもしくは水酸化バリウムである特許請求
の範囲第1項から第3項までのいずれかに記載の方法。 5 実質的に反応が行なわれた後に水またはメタノール
を添加する特許請求の範囲第1項から第4項までのいず
れかに記載の方法。[Scope of Claims] 1. An aliphatic compound characterized in that an aliphatic β-ketoester or β-diketone is treated with an alkaline earth metal hydroxide without a solvent to obtain the corresponding alkaline earth metal salt. A method for producing an alkaline earth metal salt of a β-keto compound. 2. The method according to claim 1, wherein the aliphatic β-ketoester is ethyl acetoacetate or methyl acetoacetate. 3. The method according to claim 1, wherein the aliphatic β-diketone is acetylacetone. 4. The method according to any one of claims 1 to 3, wherein the alkaline earth metal hydroxide is calcium hydroxide, magnesium hydroxide, or barium hydroxide. 5. The method according to any one of claims 1 to 4, wherein water or methanol is added after substantially the reaction has taken place.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5469176A JPS6024777B2 (en) | 1976-05-12 | 1976-05-12 | Method for producing alkaline earth metal salt of aliphatic β-keto compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5469176A JPS6024777B2 (en) | 1976-05-12 | 1976-05-12 | Method for producing alkaline earth metal salt of aliphatic β-keto compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS52136131A JPS52136131A (en) | 1977-11-14 |
JPS6024777B2 true JPS6024777B2 (en) | 1985-06-14 |
Family
ID=12977811
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5469176A Expired JPS6024777B2 (en) | 1976-05-12 | 1976-05-12 | Method for producing alkaline earth metal salt of aliphatic β-keto compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6024777B2 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19610320C2 (en) * | 1996-03-15 | 1998-01-22 | Henkel Kgaa | Process for the preparation of alkaline earth metal salts of aliphatic beta-keto compounds |
FR2775971B1 (en) * | 1998-03-12 | 2000-04-07 | Rhodia Chimie Sa | PREPARATION OF METAL SALTS OF BETA-DICARBONYL COMPOUNDS FROM METAL OXIDES |
JP2000026362A (en) * | 1998-07-10 | 2000-01-25 | Daicel Chem Ind Ltd | Production of alkaline-earth metal salt of beta-diketo compound |
FR2798381A1 (en) * | 1999-09-14 | 2001-03-16 | Rhodia Chimie Sa | Preparation of a calcium complex used as a PVC formulation stabilizer comprises reacting calcium (hydr)oxide with a beta-dicarbonyl compound in a 1-6C saturated alcohol and/or 2-6C ether |
CN105294439A (en) * | 2014-07-28 | 2016-02-03 | 天津合智化工有限责任公司 | Beta-keto ester complex and application thereof |
-
1976
- 1976-05-12 JP JP5469176A patent/JPS6024777B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS52136131A (en) | 1977-11-14 |
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