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JPS61180738A - Production of alkyl(dihydroxyphenyl)ketone - Google Patents

Production of alkyl(dihydroxyphenyl)ketone

Info

Publication number
JPS61180738A
JPS61180738A JP2132985A JP2132985A JPS61180738A JP S61180738 A JPS61180738 A JP S61180738A JP 2132985 A JP2132985 A JP 2132985A JP 2132985 A JP2132985 A JP 2132985A JP S61180738 A JPS61180738 A JP S61180738A
Authority
JP
Japan
Prior art keywords
compound
alkyl
halide
zinc
resorcin
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.)
Granted
Application number
JP2132985A
Other languages
Japanese (ja)
Other versions
JPH0225896B2 (en
Inventor
Kimiaki Tanaka
公章 田中
Shugo Matsuno
松野 修吾
Kuniaki Goto
邦明 後藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Nippon Zeon Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co Ltd filed Critical Nippon Zeon Co Ltd
Priority to JP2132985A priority Critical patent/JPS61180738A/en
Publication of JPS61180738A publication Critical patent/JPS61180738A/en
Publication of JPH0225896B2 publication Critical patent/JPH0225896B2/ja
Granted legal-status Critical Current

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PURPOSE:To obtain the titled compound by a simple operation efficiently in high quality in high yield, by reacting a resorcin compound and a lower carboxylic acid halide as raw materials in the presence of a zinc halide and an inert solvent in a heterogeneous state. CONSTITUTION:A resorcin compound shown by the formula (R1-R3 are H, or <=5C alkyl) such as resorcin, etc., is reacted with <=5C monocarboxylic acid halide such as acetic acid chloride, etc., in an inert solvent such as nitrobenzene, etc., in the presence of a zinc halide such as zinc chloride, etc., at -10-100 deg.C for 0.1-5hr, the reaction mixture is subjected to solid-liquid separation, and the prepared solid substance is washed with water, to give the aimed high- quality compound such as 2,4-dihyroxyacetophenone, etc. EFFECT:Complicated operations such as distillation, recrystallization, etc., after the reaction are not required, and separating operation can be simplified. USE:An intermediate for fine chemicals, and a raw material for drugs, agricultural chemicals, photosensitive materials, perfume, resins, etc.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明はアルキル(ジヒドロキシフェニル)ケトンの製
造法に関し、さらに詳しくは、レゾルシン化合物と低級
カルゲン酸ハライドを原料として簡単な操作で効率よく
アルキル(2,4−ジヒドロキシフェニル)ケトンを製
造する法に関する。
Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing alkyl (dihydroxyphenyl) ketones, and more specifically, the present invention relates to a method for producing alkyl (dihydroxyphenyl) ketones, and more specifically, to efficiently produce alkyl (dihydroxyphenyl) ketones by simple operations using a resorcinol compound and lower calgenic acid halide as raw materials. The present invention relates to a method for producing 2,4-dihydroxyphenyl)ketone.

(従来の技術) レゾルシン化合物と低級カルボン酸をハロゲン化亜鉛の
存在下に反応させてアルキル(2,4−ジヒドロキシフ
ェニル)ケトンを製造する方法は。
(Prior Art) A method for producing an alkyl (2,4-dihydroxyphenyl) ketone by reacting a resorcin compound and a lower carboxylic acid in the presence of zinc halide is described.

従来から公知である。例えばその具体例として。It is conventionally known. For example, as a specific example.

酢酸と塩化亜鉛の混合物を140℃まで加熱溶解し、こ
れにレゾルシンを加えて159℃まで加熱する方法(0
RGANIC5YNTHKSES Co11@ctiv
e Vol、3゜761頁)、塩化亜鉛の存在下、レゾ
ルシンと酢酸を100〜130℃で反応させる方法(%
開昭59−65039号)等が知られている。
A method of heating and dissolving a mixture of acetic acid and zinc chloride to 140°C, adding resorcin to it, and heating it to 159°C (0
RGANIC5YNTHKSES Co11@ctiv
e Vol, 3゜761), a method of reacting resorcin and acetic acid at 100 to 130°C in the presence of zinc chloride (%
1983-65039) etc. are known.

しかしながら、いずれの方法も100℃以上の高温下で
反応を行うため生成物が着色しやすく。
However, in both methods, the reaction is carried out at a high temperature of 100° C. or higher, so the products tend to be colored.

またその収率の面でも必ずしも満足できるものではなか
った。
Furthermore, the yield was not always satisfactory.

一般に低級カルボン酸の代わりに低級カルボン酸ハライ
ドを使用すれば低温下で反応させることが可能である。
Generally, if a lower carboxylic acid halide is used instead of a lower carboxylic acid, the reaction can be carried out at low temperatures.

そこで酢酸にレゾルシンを溶解させ、室温で塩化酢酸を
添加して均−系で反応させる方法を試みたところ1着色
の問題は回避しりるが、その他の副生成物が多量に生成
し、2.4−ジヒドロキシアセトフェノンの収率が低く
、更に反応後の2.4−ジヒドロキシアセトフェノンの
分離操作が煩雑になるという問題があった。
Therefore, we tried a method in which resorcinol was dissolved in acetic acid and acetic acid chloride was added at room temperature to cause a homogeneous reaction.1.The problem of coloration was avoided, but large amounts of other by-products were produced.2. There were problems in that the yield of 4-dihydroxyacetophenone was low and furthermore, the separation operation of 2,4-dihydroxyacetophenone after the reaction was complicated.

(発明が解決しようとする問題点) そこで本発明者らは、従来技術にみられる前記欠点を解
決すべく鋭意研究の結果、レゾルシン化合物と低級カル
ゲン酸ハライドの反応を不均一状態で行うと、アルキル
(2,4−ジヒドロキシフェニル)ケトンの収率が飛躍
的に向上し、また、キの後の分離操作が簡素化しうろこ
とを見い出し。
(Problems to be Solved by the Invention) Therefore, as a result of intensive research in order to solve the above-mentioned drawbacks seen in the prior art, the present inventors found that when the reaction between a resorcin compound and a lower calgenic acid halide is carried out in a heterogeneous state, It was discovered that the yield of alkyl (2,4-dihydroxyphenyl) ketone can be dramatically improved, and that the separation operation after step (i) can be simplified.

これらの知見に基づいて本発明を完成するに到った。Based on these findings, we have completed the present invention.

(問題点を解決するための手段) かくして本発明によれば、レゾルシン化合物と低級カル
デン酸ハライドをハロゲン化亜鉛及び不活性溶剤の存在
下に不均一状態で反応させアルキル(2,4−ジヒドロ
キシフェニル)ケトンヲ生成せしめたのち、固液分離を
行い1次いで得られた固形分を水洗することを特徴とす
るアルキル(2,4−ジヒドロキシフェニル)ケトンの
製造法が提供される。
(Means for Solving the Problems) Thus, according to the present invention, a resorcinol compound and a lower caldenic acid halide are reacted in a heterogeneous state in the presence of a zinc halide and an inert solvent to form an alkyl (2,4-dihydroxyphenyl) compound. ) A method for producing an alkyl (2,4-dihydroxyphenyl) ketone is provided, which comprises producing a ketone, performing solid-liquid separation, and then washing the obtained solid with water.

以下、具体的に本発明の詳細な説明する。Hereinafter, the present invention will be specifically explained in detail.

反応に供するレゾルシン化合物、低級カルボン酸ハライ
ド、ハロゲン化亜鉛及び不活性溶剤はいずれも実質的に
無水であること誌!必要である。
The resorcinol compound, lower carboxylic acid halide, zinc halide, and inert solvent used in the reaction must all be substantially anhydrous! is necessary.

本発明においで反応原料として用いられるレゾルシン化
合物とは、レゾルシンそのもの゛のほか芳香核に置換基
を有するレゾルシン誘導体をも包含するものであり、好
ましくは下記一般式で示されるものである。
The resorcinol compound used as a reaction raw material in the present invention includes not only resorcinol itself but also resorcinol derivatives having a substituent on the aromatic nucleus, and is preferably represented by the following general formula.

一般式: 〔但し、R,、R2,R3は、水素原子または炭素数5
以下のアルキル基を意味する。〕 一方、用いられる低級カルボン酸ハライドは、通常、炭
素数5以下のモノカルボン酸ハライドであり、その具体
例として酢酸クロライド、ゾロピオン酸クロライド、酪
酸クロライド、酢酸ブロマイド、酢酸アイオダイドなど
が例示される。
General formula: [However, R,, R2, R3 are hydrogen atoms or have 5 carbon atoms
It means the following alkyl group. On the other hand, the lower carboxylic acid halide used is usually a monocarboxylic acid halide having 5 or less carbon atoms, and specific examples thereof include acetic acid chloride, zolopionic acid chloride, butyric acid chloride, acetic bromide, acetic acid iodide, and the like.

また用いられるハロゲン化亜鉛の具体例としてはフッ化
亜鉛、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛があり、とくに
塩化亜鉛が賞月される。  ゛本発明で用いられる不活
性溶痢は、生成物であるアルキル(ゾヒドロΦシ′フェ
ニル)ケトン&ltして溶解度が低くかつ反応に対して
不活性なもの+あシ、その具体例として1例えばニトロ
ベンゼン、クロルベンゼン、四塩化炭素、軽油、二硫化
炭素、塩化エチレン、塩化メチレン、シクロヘキサン、
ヘキサン、クロロホルム、などが挙げられる。□ 低級カルボン酸ハライドの使用量は1通常、レゾルシン
化合物に対し当モルから5iモル使用するが、当モルか
ら2倍モルの使用が好ましい。
Specific examples of zinc halides that can be used include zinc fluoride, zinc chloride, zinc bromide, and zinc iodide, with zinc chloride being particularly preferred.゛The inert lysate used in the present invention is a product alkyl (zohydrocyphenyl)ketone &lt; which has low solubility and is inert to the reaction + reed; Nitrobenzene, chlorobenzene, carbon tetrachloride, diesel oil, carbon disulfide, ethylene chloride, methylene chloride, cyclohexane,
Examples include hexane, chloroform, etc. □ The amount of the lower carboxylic acid halide to be used is usually 1 to 5 imol per mole of the resorcinol compound, but preferably from the same mole to 2 times the mole.

ハロゲン化亜鉛の使用量も適宜選択しうるカド。The amount of zinc halide used can also be selected as appropriate.

通常、レゾルシン化合物に対して0.5倍モルから3倍
モルであシ、とく□に当モルから2倍モルの使用が好ま
しい。不活性溶剤の使用量は1通常、レゾルシン化合物
に対し当モルから20倍モルである。
Usually, the amount is 0.5 to 3 times the mole of the resorcinol compound, and it is particularly preferable to use the amount of 0.5 to 3 times the mole of the resorcinol compound. The amount of the inert solvent used is usually 1 to 20 times the molar equivalent to the resorcinol compound.

レゾルシン化合物、低級カルゲン酸ノーライ、ド。Resorcinol compounds, lower calgenic acids, de.

ハロダン化亜鉛、不活性溶剤の仕込み方法については、
何ら制約を受けない。例えば低温状態でし□ ゾルシン
化合物、低級カルゲン酸ノ1ライド、ノ10rン化亜鉛
、不活性溶剤を混合しておいて所定の温度で反応しても
よいし、又、レゾルシン化合物。
For information on how to prepare zinc halide and inert solvent,
Not subject to any restrictions. For example, a resorcin compound, a lower calgenic acid nitride, a zinc chloride, and an inert solvent may be mixed together at a low temperature and then reacted at a predetermined temperature, or a resorcin compound.

ハロダン化亜鉛、不活性溶剤を混合して所定の温度とし
た後、低級カルデン酸ハライドを添加しても差しつかえ
ない。
After mixing zinc halide and an inert solvent and bringing the mixture to a predetermined temperature, lower caldic acid halide may be added.

必要な反応温度は1通常、−10〜100℃。The required reaction temperature is usually -10 to 100°C.

好ましくは0〜60℃であり1反応時間は0.1〜5時
間である。
Preferably the temperature is 0 to 60°C and one reaction time is 0.1 to 5 hours.

本発明においては1反応終了後に反応混合物の固液分離
が行われる。固液分離の方法はとくに制限されず、濾過
分離法、静置分離法などが例示される。
In the present invention, solid-liquid separation of the reaction mixture is performed after completion of one reaction. The solid-liquid separation method is not particularly limited, and examples thereof include a filtration separation method and a static separation method.

固液分離によって得られた固形分は未反応のしゾルシン
化合物やハロダン化亜鉛を含有しているため、それらを
除去するために水による洗浄が行われ、それによって高
品質のアルキル(ジヒドロキシフェニル)ケトンが得ら
れる。水洗に際しては塩酸水溶液のような酸水溶液を用
いることが好ましく、それによって純度は一層向上する
The solid content obtained by solid-liquid separation contains unreacted solcin compounds and zinc halide, so washing with water is performed to remove them, thereby producing high-quality alkyl (dihydroxyphenyl). Ketones are obtained. When washing with water, it is preferable to use an acid aqueous solution such as an aqueous hydrochloric acid solution, thereby further improving the purity.

(発明の効果) かくして本発明によれば、反応後の蒸留、再結晶などの
煩雑な操作を避けることができ、しかも高品質のアルキ
ル(ジヒドロキシフェニル)ケトンを収率よく得ること
ができる。
(Effects of the Invention) Thus, according to the present invention, complicated operations such as post-reaction distillation and recrystallization can be avoided, and high-quality alkyl (dihydroxyphenyl) ketones can be obtained in good yield.

この様にして得られたアルキル(ジヒドロキシフェニル
)ケトンは、ファインケミカル中間体。
The alkyl (dihydroxyphenyl) ketone obtained in this way is a fine chemical intermediate.

医薬、農薬、感光材料、香料、樹脂等の原料として重要
な物質である。
It is an important substance as a raw material for medicines, agricultural chemicals, photosensitive materials, fragrances, resins, etc.

(実施例) 以下に実施例を挙げて本発明をさらに具体的に説明する
。なお、実施例中の部及びチはとくに断りのないかぎ9
重量基準である。
(Example) The present invention will be described in more detail with reference to Examples below. In addition, parts and parts in the examples are key 9 unless otherwise specified.
It is based on weight.

実施例1 攪拌装置、温度計、冷却管を装着した4つロフラスコに
レゾルシン44部、塩化亜鉛80部およびニトロベンゼ
ン300部を仕込み、40’Cまで昇温し、その温度で
0.5時間かけて塩化酢酸40部を添加し、その後0.
5時間不均−状態で攪拌を行った。
Example 1 44 parts of resorcinol, 80 parts of zinc chloride, and 300 parts of nitrobenzene were charged into a four-bottle flask equipped with a stirrer, a thermometer, and a cooling tube, heated to 40'C, and heated at that temperature for 0.5 hours. Add 40 parts of acetic acid chloride, then add 0.
Stirring was carried out in an uneven state for 5 hours.

その後、室温まで冷却して濾過したのち、18チ塩酸水
溶液150部で洗浄、濾過し1次いで乾燥して着色の非
常に少ない2,4−ジヒドロキシアセトフェノン53.
6部を得た。レゾルシンに対スる収率は8部1モルチで
あり1選択率は99チであった。得られた2、4−ジヒ
ドロキシアセトフェノンの純度は99チ以上であシ、融
点146〜147・℃であった。
Thereafter, it was cooled to room temperature and filtered, washed with 150 parts of 18-thihydrochloric acid aqueous solution, filtered, and then dried to produce 2,4-dihydroxyacetophenone with very little coloring.
I got 6 copies. The yield based on resorcinol was 8 parts and 1 mole, and the selectivity was 99 mole. The purity of the obtained 2,4-dihydroxyacetophenone was 99% or higher, and the melting point was 146-147°C.

実施例2 実施例1で用いたニトロベンゼンに代えてクロルベンゼ
ン280部を用いること以外は実施例1と同様の操作を
行い、非常に着色の少ない2.4−ジヒドロキシアセト
フェノン51.7部を得た。レゾルシンに対する収率は
85.1モルチであり1選択率は、99チであった。得
られた2、4−ジヒドロキシアセトフェノンの純度は9
9%以上で、融点は146〜147℃であった。
Example 2 The same operation as in Example 1 was performed except that 280 parts of chlorobenzene was used in place of the nitrobenzene used in Example 1, and 51.7 parts of 2,4-dihydroxyacetophenone with very little coloring was obtained. . The yield based on resorcinol was 85.1 mol and the selectivity was 99 mol. The purity of the obtained 2,4-dihydroxyacetophenone was 9
At 9% or higher, the melting point was 146-147°C.

実施例3 18チ塩酸水溶液に代えて水150部を用いて水洗する
こと以外は実施例1と同様にして実験を行った。2,4
−ジヒドロキシアセトフェノンの収率は86.8モルチ
であった。
Example 3 An experiment was conducted in the same manner as in Example 1 except that 150 parts of water was used instead of the 18-thihydrochloric acid aqueous solution for washing. 2,4
The yield of -dihydroxyacetophenone was 86.8 mol.

Claims (1)

【特許請求の範囲】[Claims] 1、レゾルシン化合物と低級カルボン酸ハライドをハロ
ゲン化亜鉛及び不活性溶剤の存在下に不均一状態で反応
させアルキル(2,4−ジヒドロキシフェニル)ケトン
を生成せしめたのち、固液分離を行い、次いで得られた
固形分を水洗することを特徴とするアルキル(2,4−
ジヒドロキシフェニル)ケトンの製造法。
1. A resorcinol compound and a lower carboxylic acid halide are reacted in a heterogeneous state in the presence of zinc halide and an inert solvent to produce an alkyl (2,4-dihydroxyphenyl) ketone, followed by solid-liquid separation. The alkyl (2,4-
Method for producing (dihydroxyphenyl)ketone.
JP2132985A 1985-02-06 1985-02-06 Production of alkyl(dihydroxyphenyl)ketone Granted JPS61180738A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2132985A JPS61180738A (en) 1985-02-06 1985-02-06 Production of alkyl(dihydroxyphenyl)ketone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2132985A JPS61180738A (en) 1985-02-06 1985-02-06 Production of alkyl(dihydroxyphenyl)ketone

Publications (2)

Publication Number Publication Date
JPS61180738A true JPS61180738A (en) 1986-08-13
JPH0225896B2 JPH0225896B2 (en) 1990-06-06

Family

ID=12052098

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2132985A Granted JPS61180738A (en) 1985-02-06 1985-02-06 Production of alkyl(dihydroxyphenyl)ketone

Country Status (1)

Country Link
JP (1) JPS61180738A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711744A1 (en) * 1994-11-08 1996-05-15 General Electric Company Method for making acyl substituted resorcinols
EP0994093A1 (en) * 1996-05-14 2000-04-19 Hoechst Marion Roussel, Ltd. Polyhydroxyphenol derivatives and preventive and therapeutic agents for bone and cartilage diseases containing the same
JP2000505479A (en) * 1996-06-14 2000-05-09 ドリット アラド New antiviral compounds
US6828350B1 (en) 1997-12-14 2004-12-07 Exegenics Inc. Modulators of cysteine protease

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711744A1 (en) * 1994-11-08 1996-05-15 General Electric Company Method for making acyl substituted resorcinols
EP0994093A1 (en) * 1996-05-14 2000-04-19 Hoechst Marion Roussel, Ltd. Polyhydroxyphenol derivatives and preventive and therapeutic agents for bone and cartilage diseases containing the same
EP0994093A4 (en) * 1996-05-14 2000-05-17 Hoechst Marion Roussel Ltd Polyhydroxyphenol derivatives and preventive and therapeutic agents for bone and cartilage diseases containing the same
JP2000505479A (en) * 1996-06-14 2000-05-09 ドリット アラド New antiviral compounds
US6828350B1 (en) 1997-12-14 2004-12-07 Exegenics Inc. Modulators of cysteine protease

Also Published As

Publication number Publication date
JPH0225896B2 (en) 1990-06-06

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