JP2592329B2 - Process for producing 2,3,5-trimethylbenzoquinone - Google Patents
Process for producing 2,3,5-trimethylbenzoquinoneInfo
- Publication number
- JP2592329B2 JP2592329B2 JP1090869A JP9086989A JP2592329B2 JP 2592329 B2 JP2592329 B2 JP 2592329B2 JP 1090869 A JP1090869 A JP 1090869A JP 9086989 A JP9086989 A JP 9086989A JP 2592329 B2 JP2592329 B2 JP 2592329B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- catalyst
- oxygen
- trimethylbenzoquinone
- present
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
- C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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、ビタミンＥなど医薬品の合成中間体として
有用である2,3,5−トリメチルベンゾキノンの製造方法
に関する。The present invention relates to a method for producing 2,3,5-trimethylbenzoquinone, which is useful as a synthetic intermediate for pharmaceuticals such as vitamin E.
2,3,5−トリメチルベンゾキノンの製造方法として
は、2,3,6−トリメチルフェノール（2,3,6−TMP）を無
機酸化剤で酸化する方法、又は触媒の存在下酸素で酸化
する方法等がある。前者の無機酸化剤を用いる方法で
は、例えば酸化剤として過マンガン酸カリウム、二酸化
マンガン、酸化鉛などが用いられておりその量は化学量
論以上必要であり、且つ低原子価状態の金属塩の処理が
必要となる。又後者の触媒存在下で酸化する方法、例え
ば触媒としてコバルト錯体を用いる方法では、反応初期
の触媒活性は高いが、触媒としての寿命は極めて短く、
工業的に使用するには難点がある。また触媒としてハロ
ゲン化銅を用いる方法、又ハロゲン化銅及びハロゲン化
リチウムを用いる方法では反応率、選択率共に高く維持
できるが種々の解決を要する欠点を有する。例えば特公
昭53−17585号、特開昭59−22513号、特開昭63−280040
号で代表される方法では、触媒を2,3,6−TMPと同重量又
はそれ以上使用しなければ収率も低く又反応速度も小さ
くなる欠点を有する。As a method for producing 2,3,5-trimethylbenzoquinone, a method of oxidizing 2,3,6-trimethylphenol (2,3,6-TMP) with an inorganic oxidant or a method of oxidizing with oxygen in the presence of a catalyst Etc. In the former method using an inorganic oxidizing agent, for example, potassium manganate, manganese dioxide, lead oxide and the like are used as the oxidizing agent, and the amount thereof is required to be stoichiometric or higher, and the metal salt in a low valence state is required. Processing is required. In the latter method of oxidizing in the presence of a catalyst, for example, a method using a cobalt complex as a catalyst, the catalytic activity in the initial stage of the reaction is high, but the life as a catalyst is extremely short,
There are drawbacks for industrial use. The method using copper halide as a catalyst or the method using copper halide and lithium halide can maintain both the reaction rate and the selectivity high, but have disadvantages that require various solutions. For example, JP-B-53-17585, JP-A-59-22513, JP-A-63-280040
The method represented by the above-mentioned method has the disadvantage that unless the catalyst is used in the same weight or more than 2,3,6-TMP, the yield is low and the reaction rate is low.
又、本願発明と近縁の発明と見られる特開昭55−7213
6号では、触媒として銅およびハロゲンイオンを使用
し、特定の水溶性ポリオキシエチレングリコール誘導体
を含む水溶液中で酸素含有ガスによる酸化を行ってい
る。しかし、この方法では、反応の選択性の低下及びポ
リオキシエチレングリコール誘導体の変質を押さえるた
め最適反応温度が45℃乃至70℃である。従って反応速度
が遅く、生産性の面でも難点がある。Japanese Patent Application Laid-Open No. 55-7213, which is considered to be a closely related invention to the present invention.
In No. 6, oxidation using an oxygen-containing gas is performed in an aqueous solution containing a specific water-soluble polyoxyethylene glycol derivative using copper and halogen ions as catalysts. However, in this method, the optimum reaction temperature is 45 ° C. to 70 ° C. in order to suppress the decrease in the selectivity of the reaction and the deterioration of the polyoxyethylene glycol derivative. Therefore, the reaction speed is slow, and there is a problem in productivity.
本発明者は上記に述べた公知技術の欠点を解決した、
より工業的実施に適した方法を確立すべく、高価な特
殊触媒を用いず市販の一般試薬が使用できること、使
用量が少ないこと、生成物が好収率で得られること、
反応速度を早くし空時収率を上げることを目的に研究
を行ない次の方法によりその目的を達することを見い出
し本発明を完成した。The present inventor has solved the above-mentioned disadvantages of the known art,
In order to establish a method suitable for more industrial practice, that a commercially available general reagent can be used without using an expensive special catalyst, that the amount used is small, that the product be obtained in good yield,
Research was conducted for the purpose of increasing the reaction rate and the space-time yield, and it was found that the purpose was achieved by the following method, and the present invention was completed.
本発明の要旨とするところは、2,3,6−TMPを、触媒と
して、塩化銅の存在下において、下記一般式で示される
ポリエチレングリコールアルキルエーテルを含有する溶
媒中で酸素又は酸素含有ガスにより酸化し、2,3,5−ト
リメチルベンゾキノンの製造するところにある。The gist of the present invention is that 2,3,6-TMP is used as a catalyst in the presence of copper chloride in a solvent containing a polyethylene glycol alkyl ether represented by the following general formula by oxygen or an oxygen-containing gas. Oxidation to produce 2,3,5-trimethylbenzoquinone.
ＲOCH2CH2 nOR′ n:1〜３ R:CH3、C2H5、C3H7、C4、H9 Ｒ′:H、CH3、C2H5、C3H7、C4H9 本発明方法での2,3,6−TMPの濃度は、反応液に対して
５〜50重量％程度で、過度に高濃度に設定すると反応中
のキノン類の析出が多くなり、操作性が悪くなる。酸化
反応に使用するガスは、酸素又はこれを不活性ガスで希
釈したガスで、空気の使用が最も経済的である。ROCH 2 CH 2 n OR ′ n: 1 to 3 R: CH 3 , C 2 H 5 , C 3 H 7 , C 4 , H 9 R ′: H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 The concentration of 2,3,6-TMP in the method of the present invention is about 5 to 50% by weight based on the reaction solution, and when the concentration is set too high, the precipitation of quinones during the reaction increases. Operability is deteriorated. The gas used for the oxidation reaction is oxygen or a gas obtained by diluting it with an inert gas, and the use of air is the most economical.
反応には、前記の一般式で示されるポリエチレングリ
コールアルキルエーテル類を含有する溶媒が使用され
る。In the reaction, a solvent containing a polyethylene glycol alkyl ether represented by the above general formula is used.
本発明の溶媒として推奨される溶媒としては、エチレ
ングリコールジメチルエーテル、エチレングリコールモ
ノメチルエーテル、ジエチレングリコールジメチルエー
テル、トリエチレングリコールジメチルエーテル等があ
るが、上記一般式で示される化合物であれば任意に選択
できる。Solvents recommended as the solvent of the present invention include ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like, and any solvent can be selected as long as it is a compound represented by the above general formula.
尚、所望により他の有機溶媒が、補助的な溶媒として
使用できる。これらの溶媒としては、ジメチルフォルム
アミド（DMF）、ジメチルアセトアミド（DMA）等の酸ア
ミド類；アセトン、メチルイソブチルケトン等のケトン
類；ジオキサンテトラヒドロフラン等の環状エーテル
類、ブチルエーテル、イソプロピルエーテル等の鎖状エ
ーテル、アセトニトル他のニトリル類；その他がある。
又ハロゲン化炭化水素、芳香族炭化水素、アルキルアル
コール等が所望により、溶媒の構成成分として使用でき
る。Incidentally, if desired, other organic solvents can be used as auxiliary solvents. Examples of these solvents include acid amides such as dimethylformamide (DMF) and dimethylacetamide (DMA); ketones such as acetone and methyl isobutyl ketone; cyclic ethers such as dioxanetetrahydrofuran; Ethers, acetonitrile and other nitriles; others.
In addition, halogenated hydrocarbons, aromatic hydrocarbons, alkyl alcohols and the like can be used as components of the solvent, if desired.
しかし、補助的に他の溶媒を使用する場合上記一般式
で示されるポリオキシエチレングリコールアルキルエー
テル類が全溶媒の50vol％以上、好ましくは、80vol％以
上含有されることが望まれる。However, when another solvent is used in an auxiliary manner, it is desired that the polyoxyethylene glycol alkyl ether represented by the above general formula is contained in 50 vol% or more, preferably 80 vol% or more of the whole solvent.
尚、反応により生成する水分は、反応に好ましい結果
をもたらすとは限らず反応の進行と共に溜去することが
望まれる。The water produced by the reaction does not always give a favorable result for the reaction, and it is desired that the water is distilled off as the reaction proceeds.
触媒として使用する塩化銅としては塩化第一銅と塩化
第二銅があり、特に塩化第二銅の使用が好ましい。Copper chloride used as a catalyst includes cuprous chloride and cupric chloride, and the use of cupric chloride is particularly preferred.
本発明において塩化銅の使用量は特に制限はないが好
ましくは使用2,3,6−TMPに対して0.01〜10倍モル、好ま
しくは0.05〜５倍モル更に好ましくは0.1〜0.5倍モルが
使用される。In the present invention, the amount of copper chloride used is not particularly limited, but is preferably 0.01 to 10 times, preferably 0.05 to 5 times, more preferably 0.1 to 0.5 times the mol of 2,3,6-TMP used. Is done.
本発明方法では、反応圧力は、常圧でも良く、空気使
用の場合は、若干の加圧が反応速度を高める点で好まし
い。In the method of the present invention, the reaction pressure may be normal pressure, and in the case of using air, slight pressurization is preferable in terms of increasing the reaction rate.
反応温度は、20℃乃至120℃、好ましくは、60乃至100
℃。反応時間は１乃至10時間。The reaction temperature is 20 ° C to 120 ° C, preferably 60 to 100 ° C.
° C. Reaction time is 1 to 10 hours.
尚、これら圧力、温度、時間に関しては、従来の技術
水準の範囲内で容易に選択できる。The pressure, temperature and time can be easily selected within the range of the conventional technical level.
本発明方法による酸化反応生成液からの2,3,6−トリ
メチルベンゾキノンの分離は、例えば、反応液を水層と
分液し、有機層を水洗後蒸溜により分離することができ
る。For the separation of 2,3,6-trimethylbenzoquinone from the oxidation reaction product solution according to the method of the present invention, for example, the reaction solution can be separated from an aqueous layer, the organic layer can be washed with water and then distilled off.
次に、本発明の実施例を、本発明の効果を示すため比
較例とともに示す。Next, examples of the present invention will be described together with comparative examples to show the effects of the present invention.
実施例１〜３ 300ml四ツ口フラスコ中に塩化銅２水和物17g（0.1モ
ル）表−１の有機溶媒50mlを入れ加温し60〜80℃に保ち
約700rpmで撹拌を行ないながら酸素ガスを流速200ml/mi
nで液面下に通気し、これに表−１の有機溶媒50mlに2,
3,6−TMP34g（0.25mol）を溶解した溶液を２時間を要し
て滴下し、滴下終了後更に2,3,6−TMPが消失する迄反応
を行ない終了後30mlの水を加え次いで100mlのトルエン
で抽出を行ないガスクロマトグラフによる分析を行ない
TMBQの収率を求めた。Examples 1 to 3 In a 300 ml four-necked flask, 17 g (0.1 mol) of copper chloride dihydrate, 50 ml of the organic solvent shown in Table 1, was heated, kept at 60 to 80 ° C., and stirred at about 700 rpm with oxygen gas. The flow rate 200ml / mi
The liquid was ventilated below the liquid surface with n, and 2,2
A solution in which 34 g (0.25 mol) of 3,6-TMP was dissolved was added dropwise over 2 hours. After completion of the addition, the reaction was further continued until 2,3,6-TMP disappeared, and after completion, 30 ml of water was added and then 100 ml. Extracted with toluene and analyzed by gas chromatography
The yield of TMBQ was determined.
比較例１ 1,000mlの四ツ口フラスコに水250ml、平均分子式CH3O
（CH2CH2O）8CH3で表わされるポリエチレングリコール
ジメチルエーテル250ml及び塩化第２銅２水和物150g
（0.88mol）を仕込んだ。80℃で約700rpmで撹拌した触
媒液に酸素ガスを330ml/minの流速で通しながら2,3,6−
TMPを１時間あたり13.6g（0.1mol）の速度で6.5時間か
けて連続的に添加した。2,3,6−TMPの添加が完了してか
ら更に３時間酸素を吹き込みながら撹拌を続けた。 Comparative Example 1 250 ml of water was placed in a 1,000 ml four-necked flask, and the average molecular formula was CH 3 O.
(CH 2 CH 2 O) 250 ml of polyethylene glycol dimethyl ether represented by 8 CH 3 and 150 g of cupric chloride dihydrate
(0.88 mol). While passing oxygen gas at a flow rate of 330 ml / min through the catalyst solution stirred at about 700 rpm at 80 ° C., 2,3,6-
TMP was added continuously at a rate of 13.6 g (0.1 mol) per hour over 6.5 hours. After the addition of 2,3,6-TMP was completed, stirring was continued for another 3 hours while blowing oxygen.
反応終了後、静置して主にTMBQからなる上層と、触媒
溶液からなる下層を分液し、更に下層からトルエンによ
りTMBQを抽出回収し、ガスクロマトグラフによる分析を
行ないTMBQの収率を求めた。本例でのTMBQの収率は90％
であった。After the completion of the reaction, the mixture was allowed to stand, the upper layer mainly composed of TMBQ and the lower layer composed of the catalyst solution were separated, and TMBQ was extracted and recovered from the lower layer with toluene, and analyzed by gas chromatography to determine the yield of TMBQ. . TMBQ yield in this example is 90%
Met.
Claims (1)
して塩化銅の存在下において、下記一般式で示されるポ
リエチレングリコールアルキルエーテルを含有する溶媒
中で酸素又は酸素含有ガスにより酸化することを特徴と
する2,3,5−トリメチルベンゾキノンの製造法。 ＲOCH2CH2 nOR′ n:1〜３ R:CH3、C2H5、C3H7、C4H9 Ｒ′:H、CH3、C2H5、C3H7、C4H9 (1) Oxidation of 2,3,6-trimethylphenol with oxygen or an oxygen-containing gas in a solvent containing a polyethylene glycol alkyl ether represented by the following general formula in the presence of copper chloride as a catalyst. Characteristic method for producing 2,3,5-trimethylbenzoquinone. ROCH 2 CH 2 n OR ′ n: 1 to 3 R: CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 R ′: H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1090869A JP2592329B2 (en) | 1989-04-12 | 1989-04-12 | Process for producing 2,3,5-trimethylbenzoquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1090869A JP2592329B2 (en) | 1989-04-12 | 1989-04-12 | Process for producing 2,3,5-trimethylbenzoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02270839A JPH02270839A (en) | 1990-11-05 |
| JP2592329B2 true JP2592329B2 (en) | 1997-03-19 |
Family
ID=14010528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1090869A Expired - Lifetime JP2592329B2 (en) | 1989-04-12 | 1989-04-12 | Process for producing 2,3,5-trimethylbenzoquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2592329B2 (en) |
-
1989
- 1989-04-12 JP JP1090869A patent/JP2592329B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02270839A (en) | 1990-11-05 |
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