JPS63258828A - Production of high-purity alpha-hydroxyketone - Google Patents
Production of high-purity alpha-hydroxyketoneInfo
- Publication number
- JPS63258828A JPS63258828A JP9416487A JP9416487A JPS63258828A JP S63258828 A JPS63258828 A JP S63258828A JP 9416487 A JP9416487 A JP 9416487A JP 9416487 A JP9416487 A JP 9416487A JP S63258828 A JPS63258828 A JP S63258828A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- acylated
- alpha
- compound
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- IBWFPYRVHYLXEU-UHFFFAOYSA-N 3-hydroxy-3-phenylbutan-2-one Chemical compound CC(=O)C(C)(O)C1=CC=CC=C1 IBWFPYRVHYLXEU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 5
- 239000000543 intermediate Substances 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 aluminum alkoxide Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000010933 acylation Effects 0.000 description 4
- 238000005917 acylation reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GKDLTXYXODKDEA-UHFFFAOYSA-N 1-phenylbutan-2-one Chemical compound CCC(=O)CC1=CC=CC=C1 GKDLTXYXODKDEA-UHFFFAOYSA-N 0.000 description 1
- BMZBEWUYETVZAG-UHFFFAOYSA-N 4-oxofuran-2-carboxylic acid Chemical compound OC(=O)C1=CC(=O)CO1 BMZBEWUYETVZAG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010021024 Hypolipidaemia Diseases 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 238000006480 benzoylation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000006242 butyrylation Effects 0.000 description 1
- 238000010514 butyrylation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000005803 octanoylation Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000006289 propionylation Effects 0.000 description 1
- 238000010515 propionylation reaction Methods 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、α−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α−ヒドロキシケトン類は、医農
薬の中間体として利用されており、例えば２−ヒドロキ
シ−３，フェニル−２−ブタノンは低脂肪血因子の１つ
である４−メチル−４−フェニル−４，５−ジヒドロ−
４−オキソフラン−２−カルボン酸の合成中間体として
有用である（アイ、エル、ジャーコブスキ１、Ｌ、Ｊｉ
ｒｋｏｖｓｋｙ、アメリカ特許第４１６９２０２号第４
２４４９５８号）。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing α-hydroxyketones. α-Hydroxyketones obtained by the method of the present invention are used as intermediates for medicines and agrochemicals. For example, 2-hydroxy-3, phenyl-2-butanone is a 4-methyl -4-phenyl-4,5-dihydro-
Useful as a synthetic intermediate for 4-oxofuran-2-carboxylic acid (I, L., Jerkowski 1, L., Ji
rkovsky, U.S. Pat. No. 4,169,202 No. 4
No. 244958).
（従来技術および問題点）
（反応式１）
反応式１に示すような転移反応による２−ヒドロキシケ
トンの製造方法はこれまでにも多くの公知例がある
（１）戸田敬、日本化学会誌２８２頁（１９８２）；
２）Ｄ、Ｄｉｅｔｅｒｉｃｈ、 Ｍｅｔｈｏｄｅｎ ｄ
ｅｒ Ｏｒｇａｎｉｓｈｅｎ Ｃｈｅｍｉｅ。(Prior art and problems) (Reaction formula 1) There are many known examples of the method for producing 2-hydroxyketone by a rearrangement reaction as shown in reaction formula 1. (1) Takashi Toda, Journal of the Chemical Society of Japan 282 Page (1982);
2) D. Dieterich, Methoden d
er Organishen Chemie.
ＢＡＮＤ ＶＩＩ ／ ２ａ、 １１１７ （１９７３
）、デー、デートリッヒ、メソーテンデルオーガニッシ
ェンヘミー）。BAND VII/2a, 1117 (1973
), De, Dietlich, Mesoutendelorganischenchemy).
上記転移反応は水酸化ナトリウム、水酸化カリウム、硫
酸、あるいはアルミニウムアルコキシドの作用により進
行する。しかしながら本反応は平衡反応であるため、い
ずれの場合も（１）及び（２）の混合物となり、更に（
１）および（２）の物理的性質は類似していることが多
く、分離精製も困難である。例えば反応式２に示すよう
に化合物（１ａ）は水酸化ナトリウムの作用により（２
ａ）を与えるが、（１ａ）と（２ａ）生成比は１０：９
０であり、ガスクロマトグラフィー、液体クロマトグラ
フィー、あるいは蒸留等で分離できない混合物で
（反応式２）
％式％（２）
ある。上記（産業上の利用分野）の項に記載したように
、（２ａ）は低脂肪血因子の１つである４−メチル−４
−フェニル−４，５−ジヒドロ−４−オキソフラン−２
−カルボン酸の有用な中間体であるが、反応式２で示す
方法で得られる（２ａ）中には分離困難な（１ａ）が含
まれているため、４−メチル−４，５−ジヒドロ−４−
オキソフラン−２−カルボン酸を合成する際、（１ａ）
が副反応を起こすと考えられる。これに対し、（２ａ）
を純度よく合成する方法として、アセトフェノンにアセ
チレンを付加させた後、水銀塩を作用させるもの（１，
Ｌ、Ｊｉｒｋｏｒｓｋｙ、アイ、エル、ジャーコブスキ
、アメリカ特許第４１６９２０２号）もあるが１、水銀
塩も用いることから、環境上の問題を考慮する必要があ
り、設備上、高コストになると考えられる。The above transfer reaction proceeds under the action of sodium hydroxide, potassium hydroxide, sulfuric acid, or aluminum alkoxide. However, since this reaction is an equilibrium reaction, it will be a mixture of (1) and (2) in both cases, and (
1) and (2) often have similar physical properties and are difficult to separate and purify. For example, as shown in reaction formula 2, compound (1a) is converted to (2) by the action of sodium hydroxide.
a), but the production ratio of (1a) and (2a) is 10:9
0, and is a mixture that cannot be separated by gas chromatography, liquid chromatography, distillation, etc. (Reaction Formula 2) % Formula % (2) As described in the above (industrial application field) section, (2a) is one of the hypolipidemia factors, 4-methyl-4
-phenyl-4,5-dihydro-4-oxofuran-2
Although it is a useful intermediate for carboxylic acid, (2a) obtained by the method shown in reaction formula 2 contains (1a), which is difficult to separate, so 4-methyl-4,5-dihydro- 4-
When synthesizing oxofuran-2-carboxylic acid, (1a)
is thought to cause side reactions. On the other hand, (2a)
A method for synthesizing with high purity is to add acetylene to acetophenone and then react with mercury salt (1,
However, since mercury salts are also used, it is necessary to consider environmental issues, and it is thought that the cost of equipment will be high.
（問題を解決するための手段）
本発明の目的は、異性体として存在する二種類のα−ヒ
ドロキシケトン類（（１）及び（２））をそれぞれ純度
よく分離する方法を提供することにある。即ち１）一般
式（１）
（式中、Ｒ１とＲ２及びＲ２とＲ３は同−或いは異なる
アルキル基、アリル基、およびアリール基を表し、Ｒ１
とＲ３は異なるアルキル基、アリル基およびアリール基
を表す。）で表される
化合物と一般式（２）
（式中、Ｒ１、Ｒ２、Ｒ３は一般式（１）で定義した通
りである。）で表される化合物の混合物ををアシル化し
た後に分離精製することを特徴とする高純度な一般式（
２）で示される化合物の製造法に関するものである。(Means for Solving the Problem) An object of the present invention is to provide a method for separating two types of α-hydroxyketones ((1) and (2)) existing as isomers with high purity. . That is, 1) General formula (1) (wherein R1 and R2 and R2 and R3 represent the same or different alkyl group, allyl group, and aryl group, and R1
and R3 represent different alkyl groups, allyl groups and aryl groups. ) and the compound represented by general formula (2) (wherein, R1, R2, and R3 are as defined in general formula (1)) are acylated and then separated and purified. A highly pure general formula (
The present invention relates to a method for producing the compound shown in 2).
一般式（１）において、Ｒ１，Ｒ２，Ｒ３はアルキル基
、アリル基あるいはアリール基を示し、更に換能基を有
してもよい。但しＲ１とＲ２およびＲ２とＲ３は同一で
あっても異なってもよいが、Ｒ１とＲ３は異なるアルキ
ル基、アリル基あるいはアリール基を表す。アルキル基
とし、具体的には、メチル基、エチル基、ｎ−プロピル
基、イソプロピル基、イソブチル基、５ｅｃ−ブチル基
、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル
基、 ５ｅｅ−ペンチル基、ｔｅｒｔ−ペンチル基、ｎ
−ヘキシル基、イソヘキシル基、５ｅｃ−ヘキシル基、
ｔｅｒｔ−ヘキシル基、ｎ、ヘプチル基、ｎ−オクチル
基なとの直鎖状又は分岐状のアルキル基があげられ、更
に二重結合、三重結合等の換能基を有してもよい。アリ
ル基として具体的にはアリル基、シンナミル基あげられ
る。アリール基としてはフェニル基、あるいは炭素数１
から８の直鎖状又は分岐状のアルキル基が置換したフェ
ニル基、あるいは、ニトロ基、アミノ基、スルホニル基
、ハロゲン原子等の換能基が置換したフェニル基があげ
られる。更にＲ１，Ｒ２およびＲ３はいずれか２つが結
合し、環構造を形成してもよい。一般式（２）にお゛け
るＲ１．Ｒ２およびＲ３は一般式（１）で規定したもの
と同様である。In general formula (1), R1, R2, and R3 represent an alkyl group, an allyl group, or an aryl group, and may further have a substituent group. However, R1 and R2 and R2 and R3 may be the same or different, and R1 and R3 represent different alkyl groups, allyl groups, or aryl groups. An alkyl group, specifically a methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, 5ec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 5ee-pentyl group, tert -pentyl group, n
-hexyl group, isohexyl group, 5ec-hexyl group,
Examples include linear or branched alkyl groups such as tert-hexyl group, n-heptyl group, and n-octyl group, and may further have a converting group such as a double bond or triple bond. Specific examples of the allyl group include an allyl group and a cinnamyl group. Aryl group is phenyl group or carbon number 1
Examples include a phenyl group substituted with a linear or branched alkyl group (8), or a phenyl group substituted with a converting group such as a nitro group, an amino group, a sulfonyl group, or a halogen atom. Furthermore, any two of R1, R2 and R3 may be bonded to form a ring structure. R1 in general formula (2). R2 and R3 are the same as defined in general formula (1).
本発明で述るアシル化とは、アセチル化、プロピオニル
化、ブチリル化、ペンタノイル化、ヘキサノイル化、ヘ
プタノイル化、オクタノイル化、ヘソブチリル化、イソ
ペンタノイル化、イソヘキサノイル化、イソヘプタノイ
ル化、３．メチルブチリル化、３−メチルヘプタノイル
化、４−メチルヘプタノイル化、ベンゾイル化等炭素数
２〜８の直鎖状及び分岐状及び芳香族のアシル基の導入
を意味し、適宜目的に応じて、選択される。アシル化の
条件としては、１）ピリジンあるいはトリエチルアミン
或いはイミダゾール等塩基の存在下酸ハライドあるいは
酸無水物を作用させる方法および２）金属ヒドリドにα
−ヒドロキシケトン類を作用させ、金属アルコラードと
した後、酸ハライドあるいは酸無水物を作用させる方法
および３）有機酸の存在下で酸無水物を作用させる方法
等があるがアシル化の方法あるいは条件を限定するもの
ではない。本発明は物理的な性質の類似する二種類α−
ヒドロキシケトン類（（１）および（２））の一方を優
先的にあるいは両者を部分的にアシル化し、物理的性質
の異なるα−ヒドロキシケトンとα−アシロキシケトン
の混合物にした後、蒸留等の方法により（１）あるいは
（２）を、分離精製をするものである。一方のα−ヒド
ロキシケトンが選択的にアシル化できる場合、アシル化
されたα−ヒドロキシケトンすなわちα−アシルオキシ
ケトンは分離精製後加水分解し、α、ヒドロキシケトン
に戻すことが可能であるので二種類のα−ヒドロキシケ
トン類（（１）及び（２））は両者とも他者から分離精
製することができる。又α−ヒドロキシケトンあるいは
α−アシロキシケトンがアシル化条件下で分解すること
も考えられるがこの場合、二種のα−ヒドロキシケトン
の一方あるいは両者の一部を分解物ととして除去し、残
るα、ヒドロキシケトン類が蒸留等の方法により分離精
製される。分離精製法は、具体的には各種クロマトクラ
フィー法、蒸留法等があるが特にこれを限定るものでは
なく、目的に応じ適宜選ばれる。Acylation mentioned in the present invention includes acetylation, propionylation, butyrylation, pentanoylation, hexanoylation, heptanoylation, octanoylation, hesobutylation, isopentanoylation, isohexanoylation, isoheptanoylation, 3. Means the introduction of linear, branched, and aromatic acyl groups having 2 to 8 carbon atoms, such as methylbutyrylation, 3-methylheptanoylation, 4-methylheptanoylation, and benzoylation, depending on the purpose. selected. The conditions for acylation include 1) a method in which an acid halide or an acid anhydride is reacted in the presence of a base such as pyridine, triethylamine, or imidazole; and 2) a method in which α is applied to a metal hydride.
-A method or conditions for acylation, such as a method in which hydroxyketones are reacted to form a metal alcoholade, and then an acid halide or an acid anhydride is reacted, and 3) a method in which an acid anhydride is reacted in the presence of an organic acid. It is not limited to. The present invention is based on two types of α-
After preferentially or partially acylating one or both of the hydroxyketones ((1) and (2)) to form a mixture of α-hydroxyketone and α-acyloxyketone with different physical properties, distillation etc. This method separates and purifies (1) or (2). If one α-hydroxyketone can be selectively acylated, the acylated α-hydroxyketone, that is, α-acyloxyketone, can be hydrolyzed after separation and purification and returned to α-hydroxyketone, so there are two types. Both of the α-hydroxyketones ((1) and (2)) can be separated and purified from others. It is also possible that α-hydroxyketone or α-acyloxyketone decomposes under acylation conditions, but in this case, one or both of the two α-hydroxyketones may be partially removed as a decomposition product, and the remaining α, hydroxyketones are separated and purified by a method such as distillation. Specific separation and purification methods include various chromatography methods, distillation methods, etc., but are not particularly limited to these methods, and are appropriately selected depending on the purpose.
（発明の効果）
本発明の方法により、安価でかつ高純度のα−ヒドロキ
シケトン類を製造することが可能となった。(Effects of the Invention) The method of the present invention has made it possible to produce inexpensive and highly pure α-hydroxyketones.
実施例１
（３−ヒドロキシ−３−フェニル−２−ブタノンの製造
法）分離不可能なα−ヒドロキシイソブチロフェノン（
１ａ）と３−ヒドロキシ−３−フェニル−２−ブタノン
（２ａ）の混合物（２，ＯＯｇ、 （ｌａ）：（２ａ）
＝ １０／９０）をピリジン（１ミリリツトル）および
トルエン（１ミリリツトル）に溶がし、更にアセチルク
ロリド（０，９ミリリツトル）を加え、室温下で８時間
撹はんした。１規定塩酸水溶液で反応を停止し、エーテ
ル抽出した。エーテルを減圧留去し、蒸留することによ
り３−ヒドロキシ−３−フェニル−２−ブタノン（１，
７５グラム、１３０°Ｃ１０，０７ｍｍＨｇ）が得られ
た。この場合、アセチル化物はみられず、構造不明な高
沸点物が残香に残った。Example 1 (Process for producing 3-hydroxy-3-phenyl-2-butanone) Inseparable α-hydroxyisobutyrophenone (
1a) and 3-hydroxy-3-phenyl-2-butanone (2a) (2,OOg, (la): (2a)
= 10/90) was dissolved in pyridine (1 ml) and toluene (1 ml), acetyl chloride (0.9 ml) was added, and the mixture was stirred at room temperature for 8 hours. The reaction was stopped with a 1N aqueous hydrochloric acid solution and extracted with ether. By removing the ether under reduced pressure and distilling it, 3-hydroxy-3-phenyl-2-butanone (1,
75 grams, 130°C, 10.07 mmHg) was obtained. In this case, no acetylated product was observed, and a high-boiling point product of unknown structure remained in the residual aroma.
実施例２
実施例１においてアセチルクロリド（０，９ミリリツト
ル）のかわりにベンゾイルクロリド（１，７グラム）を
用いた他は実施例１と同様の操作を行った。反応疎精製
物を蒸留することにより３−ヒドロキシ−３゜フェニル
−２−ブタノン（１，５０グラム）が得られた。Example 2 The same procedure as in Example 1 was carried out except that benzoyl chloride (1.7 grams) was used instead of acetyl chloride (0.9 milliliters). 3-Hydroxy-3°phenyl-2-butanone (1.50 grams) was obtained by distilling the reaction product.
Claims (1)
は異なるアルキル基、アリル基、およびアリール基を表
し、Ｒ＾１とＲ＾３は異なるアルキル基、アリル基およ
びアリール基を表す。）で表される化合物と 一般式（２） ▲数式、化学式、表等があります▼（２） （式中、Ｒ＾１、Ｒ＾２、Ｒ＾３は一般式（１）で定義
した通りである。）で表される化合物の混合物をアシル
化した後に分離精製することを特徴とする高純度な一般
式（２）で示される化合物の製造法 ２）一般式（１）で表される化合物が２−ヒドロキシイ
ソブチロフェノンであり、一般式（２）で表される化合
物が３−ヒドロキ−３−フェニル−２−ブタノンである
ことを特徴とする特許請求の範囲第一項記載の方法。[Claims] 1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, R^1 and R^2 and R^2 and R^3 are the same or different alkyl group, allyl group, and aryl group, and R^1 and R^3 represent different alkyl groups, allyl groups, and aryl groups) and general formula (2) ▲Mathematical formula, chemical formula, table, etc. ▼ (2) (In the formula, R^1, R^2, and R^3 are as defined in general formula (1).) A mixture of compounds represented by the formula (1) is acylated and then separated and purified. 2) The compound represented by general formula (1) is 2-hydroxyisobutyrophenone, and the compound represented by general formula (2) is A method according to claim 1, characterized in that the compound is 3-hydroxy-3-phenyl-2-butanone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9416487A JPS63258828A (en) | 1987-04-16 | 1987-04-16 | Production of high-purity alpha-hydroxyketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9416487A JPS63258828A (en) | 1987-04-16 | 1987-04-16 | Production of high-purity alpha-hydroxyketone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63258828A true JPS63258828A (en) | 1988-10-26 |
Family
ID=14102726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9416487A Pending JPS63258828A (en) | 1987-04-16 | 1987-04-16 | Production of high-purity alpha-hydroxyketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63258828A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011516590A (en) * | 2008-04-14 | 2011-05-26 | ロンザ リミテッド | Purification method of α-ketoester |
-
1987
- 1987-04-16 JP JP9416487A patent/JPS63258828A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011516590A (en) * | 2008-04-14 | 2011-05-26 | ロンザ リミテッド | Purification method of α-ketoester |
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