JPS5929566B2 - Production method of dioxybenzene monoalkyl ether - Google Patents
Production method of dioxybenzene monoalkyl etherInfo
- Publication number
- JPS5929566B2 JPS5929566B2 JP50013970A JP1397075A JPS5929566B2 JP S5929566 B2 JPS5929566 B2 JP S5929566B2 JP 50013970 A JP50013970 A JP 50013970A JP 1397075 A JP1397075 A JP 1397075A JP S5929566 B2 JPS5929566 B2 JP S5929566B2
- Authority
- JP
- Japan
- Prior art keywords
- dioxybenzene
- monoalkyl ether
- production method
- reaction
- monoalkyl
- 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
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
- 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】
この発明は、グアャコール、グエトール等のようなジオ
キシベンゼンモノアルキルエーテルを高い選択率で得る
ための改良された方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved process for obtaining dioxybenzene monoalkyl ethers such as guaiacol, guetol, etc. with high selectivity.
従来、ジオキシベンゼンモノアルキルエーテルが、ジオ
キシベンゼン（カテコール、ハイドロキノン、レゾルシ
ン）とハロゲン化アルキルとを了ルカリ金属の水酸化物
、炭酸塩または重炭酸塩の存在下、水と炭化水素とから
なる混合溶剤中で、加圧下、８０〜１６０℃の温度で１
〜１０時間反応させることによつて得られることは公知
となつている。例えば、特開昭４９−２４９２８号公報
においては、アルカリにカセイソーダと炭酸ソーダとを
併用し、溶媒に水とトルエンとを使用しジアルキルエー
テル（ベラトロール、ジエトキシベンゼンなど）の副生
の抑制を試みているが、モノアルキルエーテルの選択率
は９４〜９７％と低い。また、英国特許第１２７７１８
６号公報においては、ジオキシベンゼンに対してトリエ
タノールアミンまたはトリエチルアミンを３．３〜４．
８モル％添加して反応させてはいるものの、なおモノア
ルキルエーテルの選択率は９１〜９８％と低い。このよ
うに従来法ではモノアルキルエーテルのほかに目的とし
ないジアルキルエーテルが可成りな量で副生し、それら
の分離が困難であることによつて高純度のジオキシベン
ゼンモノアルキルエーテルを収得する上で支障があつた
。この発明は、高い選択率でジオキシペンチッモノアル
キルエーテルを収得することができる改良方法を提供す
ることを目的としたものであり、さらには複雑な操作を
ともなう抽出分離方法を適用しなくても高純度のジオキ
シベンゼンモノアルキルエーテルが得られ、この発明は
工業上極めて有利な方法である。Traditionally, dioxybenzene monoalkyl ethers have been used to prepare dioxybenzenes (catechol, hydroquinone, resorcinol) and alkyl halides from water and hydrocarbons in the presence of alkali metal hydroxides, carbonates or bicarbonates. 1 at a temperature of 80 to 160°C under pressure in a mixed solvent of
It is known that it can be obtained by reacting for up to 10 hours. For example, in JP-A No. 49-24928, an attempt was made to suppress the by-product of dialkyl ethers (veratrol, diethoxybenzene, etc.) by using caustic soda and soda carbonate together as an alkali, and using water and toluene as solvents. However, the selectivity of monoalkyl ether is as low as 94-97%. Also, British Patent No. 127718
In Publication No. 6, triethanolamine or triethylamine is added to dioxybenzene in a ratio of 3.3 to 4.
Although the reaction was carried out by adding 8 mol %, the selectivity of the monoalkyl ether was still as low as 91 to 98%. In this way, in the conventional method, in addition to monoalkyl ether, a considerable amount of unintended dialkyl ether is produced as a by-product, and it is difficult to separate them, making it difficult to obtain high-purity dioxybenzene monoalkyl ether. There was a problem at the top. The purpose of the present invention is to provide an improved method that can obtain dioxypentyl monoalkyl ether with high selectivity, and furthermore, does not require the application of extraction and separation methods that involve complicated operations. Also, highly pure dioxybenzene monoalkyl ether can be obtained, and this invention is an extremely advantageous method industrially.
すなわち、この発明は、ジオキシベンゼンとハロゲン化
アルキルとをアルカリ金属の水酸化物、炭酸塩または重
炭酸塩の存在下、水と炭化水素とからなる混合溶剤中で
、加圧下、８０〜１６０℃の温度で１〜１０時間反応さ
せてジオキシベンゼンモノアルキルエーテルをつくる方
法において、鉱酸のアンモニウム塩を添加することを特
徴とするジオキシベンゼンモノアルキルエーテルの製法
に関する。That is, in the present invention, dioxybenzene and an alkyl halide are mixed under pressure in a mixed solvent of water and a hydrocarbon in the presence of an alkali metal hydroxide, carbonate, or bicarbonate. The present invention relates to a method for producing dioxybenzene monoalkyl ether, which is characterized in that an ammonium salt of a mineral acid is added in the method of producing dioxybenzene monoalkyl ether by reacting at a temperature of 1 to 10 hours at a temperature of .degree.
この発明の方法におけるジオキシベンゼンとはカテコー
ル、レゾルシンまたはヒドロキノンを意味する。Dioxybenzene in the method of this invention means catechol, resorcinol or hydroquinone.
使用できるハロゲン化アルキルの例には、炭素数１〜３
の塩化メチル、塩化エチル、塩化プロピル、臭化メチル
、臭化エチル、臭化プロピル等がある。Examples of alkyl halides that can be used include those having 1 to 3 carbon atoms;
Examples include methyl chloride, ethyl chloride, propyl chloride, methyl bromide, ethyl bromide, and propyl bromide.
また、水酸化物、炭酸塩または重炭酸塩として使用する
アルカリ金属の例には、リチウム、カリウムまたはナト
リウム等がある。Examples of alkali metals used as hydroxides, carbonates or bicarbonates include lithium, potassium or sodium.
ハロゲン化アルキルの使用割合は、ジオキシベンゼン１
モルに対して１．０〜１．２モルが好適である。The ratio of alkyl halide used is 1 part dioxybenzene.
1.0 to 1.2 moles per mole is suitable.
アルカリ金属化合物の使用割合は、同じくジオキシベン
ゼン１モルに対してアルカリ金属換算１．００〜１．１
５モルが好適である。アルカリ金属化合物のうち、水酸
化物を使用するよりも炭酸塩または重炭酸塩を使用する
方が、ジアルキルエーテルの副生が少なくなる。The ratio of alkali metal compound used is 1.00 to 1.1 in terms of alkali metal per mole of dioxybenzene.
5 mol is preferred. Among alkali metal compounds, the use of carbonates or bicarbonates produces fewer dialkyl ether by-products than the use of hydroxides.
水との混合溶剤で使用する炭化水素の例には、ベンゼン
、トルエン、キシレン等がある。Examples of hydrocarbons used in mixed solvents with water include benzene, toluene, and xylene.
水は、反応で使用するアルカリ化合物、中間生成物のジ
オキシベンゼンモノアルカリ塩および反応生成物のハロ
ゲン化アルカリを溶かし、炭化水素はジオキシベンゼン
および反応生成物のジオキシベンゼンモノアルキルエー
テルを溶かす作用をもつている。したがつて、反応原料
の量によつて溶剤の混合割合、使用割合はおのずから容
易に決定される。例えば、水と炭化水素の混合割合は、
重量で１：０．１〜３、使用割合はジオキシベンゼンに
対して重量で１：０．５〜５が好適である。この発明の
方法で、モノアルキルエーテルの選択率を向上させるた
めに添加使用する鉱酸のアンモニウム塩としては、塩酸
、硫酸、硝酸、リン酸、炭酸などのような鉱酸のアンモ
ニウム塩が挙げられ、具体例にはＮＨ４Ｃｌ．（Ｎｌｉ
ｌ）ＨＳＯ４、（ＮＨ４）２Ｓ０ぃＮＨ４ＮＯ３、ＮＨ
４Ｈ２ＰＯ３、（ＮＨ４）２ＨＰ０３（ＮＨ４）３Ｐ０
３、ＮＨ４ＨＣＯ３、（ＮＨ４）２Ｃ０３などがある。Water dissolves the alkali compound used in the reaction, the intermediate product dioxybenzene monoalkyl salt, and the reaction product alkali halide, and the hydrocarbon dissolves dioxybenzene and the reaction product dioxybenzene monoalkyl ether. It has an effect. Therefore, the mixing ratio and usage ratio of the solvent can be easily determined depending on the amount of the reaction raw materials. For example, the mixing ratio of water and hydrocarbons is
The preferred ratio is 1:0.1 to 3 by weight, and the ratio of use to dioxybenzene is 1:0.5 to 5 by weight. In the method of this invention, the ammonium salts of mineral acids added and used to improve the selectivity of monoalkyl ethers include ammonium salts of mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, etc. , specific examples include NH4Cl. (Nli
l) HSO4, (NH4)2S0iNH4NO3, NH
4H2PO3, (NH4)2HP03 (NH4)3P0
3, NH4HCO3, (NH4)2C03, etc.
これらは単独で、または２種以上を混合して使用するこ
とができ、好適な添加量はジオキシベンゼン１モル当り
０．１〜０．０２モルである。反応は、８０〜１６０℃
の温度、好ましくは１００〜１５０℃の温度で１〜１０
時間行なわせる。その間、反応系の圧力は、自然発生圧
力に維持する。この発明の方法によれば、ジオキシベン
ゼンモノアルキルエーテルが１回の反応で９９％以上の
高選択率で再現性よく取得できる。These can be used alone or in combination of two or more, and the preferred amount added is 0.1 to 0.02 mol per 1 mol of dioxybenzene. The reaction is carried out at 80-160℃
1 to 10 at a temperature of 100 to 150 °C, preferably 100 to 150 °C.
Let time take its course. During this time, the pressure of the reaction system is maintained at a naturally occurring pressure. According to the method of the present invention, dioxybenzene monoalkyl ether can be obtained with high selectivity of 99% or more and with good reproducibility in one reaction.
この発明の方法は、バツチ式でも連続式でも実施できる
。The method of the invention can be carried out either batchwise or continuously.
反応生成物のジオキシベンゼンモノアルキルエーテルは
、香料、医薬等の原料として重要な化合物である。The reaction product, dioxybenzene monoalkyl ether, is an important compound as a raw material for perfumes, medicines, etc.
次にこの発明の実施例を比較例と対照させて示す。Next, examples of the present invention will be shown in comparison with comparative examples.
実施例 １〜６カテコールモノアルキルエーテルをつく
るためにカテコールとカセイソーダとまたはこれと炭酸
ソーダと塩化メチルまたは塩化エチルとを、内容積５０
０ｍ１のオートクレーブ沖で鉱酸のアンモニウム塩を添
加して第１表に示したような条件下で攪拌しながら反応
させた。Examples 1 to 6 To prepare catechol monoalkyl ether, catechol and caustic soda, or this and sodium carbonate, and methyl chloride or ethyl chloride were mixed in an internal volume of 50
An ammonium salt of a mineral acid was added to the autoclave of 0 ml, and the reaction was carried out with stirring under the conditions shown in Table 1.
カテコールは０．５０モル使用し、また水１３０ｍｅお
よびトルエン１３０ｍ１からなる混合溶剤を使用した。0.50 mol of catechol was used, and a mixed solvent consisting of 130 ml of water and 130 ml of toluene was used.
反応完了後は、公知法にしたがつてＰＨ２〜６に調整後
、溶剤（ＭＩＢＫ）で抽出した。After the reaction was completed, the pH was adjusted to 2 to 6 according to a known method, and then extracted with a solvent (MIBK).
結果を第１表に示す。The results are shown in Table 1.
比較例 １〜４
鉱酸のアンモニウム塩の添加を行なわなかつたほかは、
実施例に準じて第２表に示したような反木＼．、条件で
実施した。Comparative Examples 1 to 4 Except for not adding the ammonium salt of mineral acid,
According to the examples, the rolled wood shown in Table 2 was prepared. It was conducted under the following conditions.
結果も第２表中にあわせて示す。The results are also shown in Table 2.
Claims (1)
リ金属の水酸化物、炭酸塩または重炭酸塩の存在下、水
と炭化水素とからなる混合溶剤中で、加圧下、８０〜１
６０℃の温度で１〜１０時間反応させてジオキシベンゼ
ンモノアルキルエーテルをつくる方法において、鉱酸の
アンモニウム塩を添加することを特徴とするジオキシベ
ンゼンモノアルキルエーテルの製法。1. Dioxybenzene and alkyl halide are mixed under pressure in a mixed solvent of water and hydrocarbon in the presence of an alkali metal hydroxide, carbonate or bicarbonate, under pressure of 80 to 1
A method for producing dioxybenzene monoalkyl ether, which comprises adding an ammonium salt of a mineral acid in the method of producing dioxybenzene monoalkyl ether by reacting at a temperature of 60° C. for 1 to 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50013970A JPS5929566B2 (en) | 1975-02-04 | 1975-02-04 | Production method of dioxybenzene monoalkyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50013970A JPS5929566B2 (en) | 1975-02-04 | 1975-02-04 | Production method of dioxybenzene monoalkyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5188930A JPS5188930A (en) | 1976-08-04 |
| JPS5929566B2 true JPS5929566B2 (en) | 1984-07-21 |
Family
ID=11848067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50013970A Expired JPS5929566B2 (en) | 1975-02-04 | 1975-02-04 | Production method of dioxybenzene monoalkyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5929566B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61153412A (en) * | 1984-12-27 | 1986-07-12 | Matsushita Electric Ind Co Ltd | Ignition device |
| JPS6312019U (en) * | 1986-06-30 | 1988-01-26 | ||
| JPS6312018U (en) * | 1986-06-30 | 1988-01-26 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5437161A (en) * | 1977-08-30 | 1979-03-19 | Showa Electric Wire & Cable Co Ltd | Fireproof putty |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4924928A (en) * | 1972-07-03 | 1974-03-05 |
-
1975
- 1975-02-04 JP JP50013970A patent/JPS5929566B2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4924928A (en) * | 1972-07-03 | 1974-03-05 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61153412A (en) * | 1984-12-27 | 1986-07-12 | Matsushita Electric Ind Co Ltd | Ignition device |
| JPS6312019U (en) * | 1986-06-30 | 1988-01-26 | ||
| JPS6312018U (en) * | 1986-06-30 | 1988-01-26 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5188930A (en) | 1976-08-04 |
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