JPH0678262B2 - Process for producing α-hydroxyketones - Google Patents
Process for producing α-hydroxyketonesInfo
- Publication number
- JPH0678262B2 JPH0678262B2 JP61150522A JP15052286A JPH0678262B2 JP H0678262 B2 JPH0678262 B2 JP H0678262B2 JP 61150522 A JP61150522 A JP 61150522A JP 15052286 A JP15052286 A JP 15052286A JP H0678262 B2 JPH0678262 B2 JP H0678262B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- reaction
- reaction temperature
- hydroxyketones
- formula
- 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
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、a-ヒドロキシケトン類の製法に関する。本発
明の方法で得られるa-ヒドロキシケトン類は、例えば不
飽和化合物の光重合開始剤として有用な物質である。TECHNICAL FIELD The present invention relates to a method for producing a-hydroxyketones. The a-hydroxyketones obtained by the method of the present invention are substances useful as photopolymerization initiators for unsaturated compounds, for example.
（従来技術及び問題点） a-ハロケトンのアルカリ触媒下での加水分解反応では、
目的の加水分解の他に脱離反応や異性化反応などの副反
応が起こる事が知られており、その為ギ酸カリウムある
いは、酢酸カリウムによりそのエステル体とした後、ア
ルカリ加水分解を行うといった二段階の反応が試みられ
ているが満足な収率で目的物が得られていなかった。
（メソーデン デァ オルガニッシェン ヘミー（Meth
oden der organischen Chemie、第VII/2c巻、2173頁（1
977））また、このような副反応を防ぎ、目的のa-ヒド
ロキシケトンを得るために相間移動触媒の存在下で加水
分解を行う方法が提唱されている。しかしながらこの方
法では、相間移動触媒といった本来生成物とは無用の高
価な触媒を使用しなければならないといった経済的不利
益及び操作の繁雑さがあった。(Prior Art and Problems) In the hydrolysis reaction of a-haloketone under an alkali catalyst,
It is known that side reactions such as elimination reaction and isomerization reaction occur in addition to the intended hydrolysis. Therefore, after making the ester form with potassium formate or potassium acetate, alkali hydrolysis is performed. Attempts were made to carry out a stepwise reaction, but the desired product was not obtained in a satisfactory yield.
(Methden Da Organischen Hemy (Meth
oden der organischen Chemie, Volume VII / 2c, page 2173 (1
977)) Also, a method has been proposed in which hydrolysis is carried out in the presence of a phase transfer catalyst in order to prevent such side reactions and obtain the desired a-hydroxyketone. However, this method has an economic disadvantage that an expensive catalyst such as a phase transfer catalyst, which is unnecessary for the original product, must be used, and the operation is complicated.
（本発明の構成） 本発明は、一般式 （但し、式中R1、R2は、低級アルキル基を意味する。Ｘ
は、ハロゲン原子を示す。）で表されるa-ハロケトンを
アルカリ金属の水酸化物のみの存在下、反応温度60℃以
下で加水分解することを特徴とする一般式 （但し、式中R1及びR2は、一般式（Ｉ）で規定したもの
と同様である）で表されるa-ヒドロキシケトン類の製法
に関するものである。(Structure of the present invention) The present invention has the general formula (However, R 1 and R 2 in the formula mean a lower alkyl group. X
Represents a halogen atom. ) Is a general formula characterized by hydrolyzing a-haloketone at a reaction temperature of 60 ° C or lower in the presence of only an alkali metal hydroxide. (However, R 1 and R 2 in the formula are the same as those defined in the general formula (I)) and relate to a process for producing an a-hydroxyketone.
一般式（Ｉ）において、R1は、メチル基、エチル基、n-
プロピル基、イソプロピル基、n-ブチル基、イソブチル
基、sec-ブチル基、tert-ブチル基又は、n-ペンチル基
などの炭素数１から５の直鎖状又は分枝状のアルキル基
を示す。R2における低級アルキル基とは、R1で例示され
た炭素数１から５の直鎖状又は分枝状アルキル基を意味
する。またＸは、ハロゲン原子であり、塩素原子、臭素
原子又はヨウ素原子を例示することができる。一般式
（II）におけるR1及びR2は、一般式（Ｉ）で規定したも
のと同様である。In the general formula (I), R 1 is a methyl group, an ethyl group, n-
A linear or branched alkyl group having 1 to 5 carbon atoms such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, or n-pentyl group is shown. The lower alkyl group for R 2 means a linear or branched alkyl group having 1 to 5 carbon atoms, which is exemplified for R 1 . X is a halogen atom, and examples thereof include a chlorine atom, a bromine atom and an iodine atom. R 1 and R 2 in the general formula (II) are the same as those defined in the general formula (I).
（問題を解決するための手段） 本発明の目的は、光重合開始剤等に有用なa-ヒドロキシ
ケトン類を上記の種々の問題点を改善して効率的かつ簡
便に得る方法を提供することにある。(Means for Solving Problems) An object of the present invention is to provide a method for efficiently and simply obtaining a-hydroxyketones useful as a photopolymerization initiator and the like by improving the above various problems. It is in.
本発明の実施態様について以下説明する。一般式（Ｉ）
のa-ハロケトンをアルカリ金属の水酸化物及び／又は炭
酸塩の水溶液に分散するか又は、アルコール類あるい
は、水に可溶な極性溶媒の共存下溶解状態で反応しても
構わない。ここで用いるアルカリ金属の水酸化物として
は、水酸化リチウム、水酸化カリウム又は、水酸化ナト
リウムなどが好適な例として挙げることができる。また
炭酸塩も同様に、炭酸リチウム、炭酸カリウム又は、炭
酸ナトリウム及びこれらの酸性塩を例示できる。これら
のアルカリ金属塩の濃度は、特に限定されないが、0.5
規定から8.0規定が反応速度の面から推奨できる。Embodiments of the present invention will be described below. General formula (I)
The a-haloketone may be dispersed in an aqueous solution of an alkali metal hydroxide and / or carbonate, or may be reacted in a dissolved state in the presence of an alcohol or a water-soluble polar solvent. Suitable examples of the alkali metal hydroxide used here include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like. Similarly, the carbonate may be exemplified by lithium carbonate, potassium carbonate, sodium carbonate and their acidic salts. The concentration of these alkali metal salts is not particularly limited, but is 0.5
A regulation of 8.0 is recommended in terms of reaction rate.
本発明の方法では、公知方法の如く相間移動触媒などの
添加物は、特に必要としないが、反応温度が重要な要因
である。即ち、反応温度を60℃以下、好ましくは、20℃
から50℃を保ち反応することが肝要であり60℃以上の反
応温度では、比較例に示す如く異性化体の副生が顕著に
あらわれるので好ましくない。In the method of the present invention, an additive such as a phase transfer catalyst is not particularly required as in the known method, but the reaction temperature is an important factor. That is, the reaction temperature is 60 ℃ or less, preferably 20 ℃
Therefore, it is important to carry out the reaction at a temperature of 50 ° C to 50 ° C. At a reaction temperature of 60 ° C or higher, by-products of isomers are remarkably produced as shown in Comparative Examples, which is not preferable.
反応時間は、反応温度やアルカリ金属塩の濃度などによ
り異なるが、数時間から数日を要する。このようにして
得られた反応粗液に適当な溶剤を添加し抽出するか、不
均一系であればそのまま分液した後、常法により精製す
ることにより、目的のa-ヒドロキシケトン類を得ること
ができる。Although the reaction time varies depending on the reaction temperature and the concentration of the alkali metal salt, it takes several hours to several days. An appropriate solvent is added to the reaction crude liquid thus obtained for extraction, or if it is a heterogeneous system, it is separated as it is, and then purified by a conventional method to obtain the target a-hydroxyketones. be able to.
（発明の効果） 本発明の方法により、公知例にみられるような相間移動
触媒など高価な試薬を必要とせず、反応温度を60℃以下
に保つのみといった極めて簡単な操作で目的のa-ヒドロ
キシケトン類を製造することが可能になった。また、不
要の添加物の混入がないため反応後の単離操作は極めて
簡便であるといった優位性も強調できる。(Effects of the Invention) The method of the present invention does not require expensive reagents such as phase transfer catalysts as found in known examples, and only requires keeping the reaction temperature at 60 ° C. or less, and the desired a-hydroxy It has become possible to produce ketones. Further, it is possible to emphasize the advantage that the isolation operation after the reaction is extremely simple because no unnecessary additives are mixed.
実施例１ a-クロロイソブチロフェノン1.8gを2.5Nの水酸化ナトリ
ウム水溶液に分散させ、反応液を50℃に保ち、6.5次時
間はんした。反応終了後、ベンゼンを加え、分液後上層
の溶媒を除去した。得られた残査を減圧蒸留し、1.56g
のa-ヒドロキシイソブチロフェノンが得られた（収率96
％）。Example 1 1.8 g of a-chloroisobutyrophenone was dispersed in a 2.5N aqueous sodium hydroxide solution, and the reaction solution was kept at 50 ° C. and stirred for 6.5 hours. After completion of the reaction, benzene was added, and after liquid separation, the upper layer solvent was removed. The residue obtained was distilled under reduced pressure to give 1.56 g.
A-hydroxyisobutyrophenone was obtained (yield 96
%).
実施例２ 実施例１において反応温度50℃、反応時間6.5時間を反
応温度25℃、反応時間３日間に変えた他は、実施例１と
同様の操作を行ったところ、81％の収率でa-ヒドロキシ
イソブチロフェノンが得られた。Example 2 The same operation as in Example 1 was carried out except that the reaction temperature was 50 ° C. and the reaction time was 6.5 hours, and the reaction temperature was 25 ° C. and the reaction time was 3 days. a-Hydroxyisobutyrophenone was obtained.
実施例３ 5Nの水酸化ナトリウム水溶液30mlにメタノール30ml加え
た溶液にa-クロロイソブチロフェノン1.8gを溶解し、25
℃で３日間反応した。メタノールを除去後、実施例１と
同様の操作により精製し、60％の収率でa-ヒドロキシイ
ソブチロフェノンを得た。Example 3 1.8 g of a-chloroisobutyrophenone was dissolved in a solution obtained by adding 30 ml of methanol to 30 ml of a 5N sodium hydroxide aqueous solution,
Reacted at ℃ for 3 days. After removing methanol, purification was carried out in the same manner as in Example 1 to obtain a-hydroxyisobutyrophenone in a yield of 60%.
比較例 a-クロロイソブチロフェノン1.8gを2.5Nの水酸化ナトリ
ウムに分散させ反応温度90℃で６時間反応させたとこ
ろ、90％の収率で生成物が得られたが、そのうち80％
は、異性体の3-ヒドロキシ‐3-フェニル‐2-ブタノン
で、20％がa-ヒドロキシイソブチロフェノンであった。Comparative Example a-Chloroisobutyrophenone (1.8 g) was dispersed in 2.5 N sodium hydroxide and reacted at a reaction temperature of 90 ° C for 6 hours to obtain a product in a yield of 90%.
Was the isomeric 3-hydroxy-3-phenyl-2-butanone, 20% a-hydroxyisobutyrophenone.
Claims (2)
は、ハロゲン原子をしめす。）で表されるα−ハロケト
ンをアルカリ金属の水酸化物のみの存在下反応温度60℃
以下で加水分解することを特徴とする一般式 （但し式中R1及びR2は、一般式（Ｉ）で規定したものと
同様である）で表されるα−ヒドロキシケトン類の製法1. A general formula (However, in the formula, R 1 and R 2 mean a lower alkyl group. X
Indicates a halogen atom. ) In the presence of an alkali metal hydroxide alone at a reaction temperature of 60 ° C.
General formula characterized by being hydrolyzed below (However, R 1 and R 2 in the formula are the same as those defined in the general formula (I))
である特許請求範囲第１項記載の製法2. The method according to claim 1, wherein R 1 and R 2 in the general formula (I) are methyl groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61150522A JPH0678262B2 (en) | 1986-06-26 | 1986-06-26 | Process for producing α-hydroxyketones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61150522A JPH0678262B2 (en) | 1986-06-26 | 1986-06-26 | Process for producing α-hydroxyketones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS635050A JPS635050A (en) | 1988-01-11 |
| JPH0678262B2 true JPH0678262B2 (en) | 1994-10-05 |
Family
ID=15498704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61150522A Expired - Lifetime JPH0678262B2 (en) | 1986-06-26 | 1986-06-26 | Process for producing α-hydroxyketones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0678262B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG71201A1 (en) * | 1998-04-20 | 2000-03-21 | Givaudan Roure Int | Hydroxa-methyl-hexanones |
| EP0952140B1 (en) * | 1998-04-20 | 2004-04-28 | Givaudan SA | 2-Hydroxy-5-methyl-hexan-3-one and 3-hydroxy-5-methyl-hexan-2-one |
| CN115894202B (en) * | 2022-12-06 | 2024-06-28 | 湖南久日新材料有限公司 | Method for treating residue of photo-initiator 1173 distillation kettle |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4097671A (en) * | 1975-08-28 | 1978-06-27 | General Electric Company | Dihydrooxadiazinones and method for making |
-
1986
- 1986-06-26 JP JP61150522A patent/JPH0678262B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS635050A (en) | 1988-01-11 |
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