JPH01238552A - Production of 2,3,5-trimethylbenzoquinone - Google Patents
Production of 2,3,5-trimethylbenzoquinoneInfo
- Publication number
- JPH01238552A JPH01238552A JP63062878A JP6287888A JPH01238552A JP H01238552 A JPH01238552 A JP H01238552A JP 63062878 A JP63062878 A JP 63062878A JP 6287888 A JP6287888 A JP 6287888A JP H01238552 A JPH01238552 A JP H01238552A
- Authority
- JP
- Japan
- Prior art keywords
- oxidizing agent
- trimethylbenzoquinone
- trimethylphenol
- reaction
- heteropolyacid
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- QIXDHVDGPXBRRD-UHFFFAOYSA-N 2,3,5-trimethylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C(C)=C(C)C1=O QIXDHVDGPXBRRD-UHFFFAOYSA-N 0.000 title claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 235000001815 DL-alpha-tocopherol Nutrition 0.000 description 1
- 239000011627 DL-alpha-tocopherol Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 etc. Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
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)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、リンまたはケイ素を中心元素とし、モリブデ
ンまたはタングステンを含むヘテロポリ酸を酸化触媒と
して使用する２、３．５−トリメチルベンゾキノンの製
造方法に関するものである。Detailed Description of the Invention [Technical Field] The present invention relates to a method for producing 2,3,5-trimethylbenzoquinone using a heteropolyacid containing phosphorus or silicon as a central element and containing molybdenum or tungsten as an oxidation catalyst. be.
さらに詳しくは、リンまたはケイ素を中心元素とし、モ
リブデンまたはタングステンを含むヘテロポリ酸を触媒
として過酸化水素を酸化剤として用いて２，３．６−ト
リメチルフェノールを酸化して効率よ＜２，３．５−）
−リメチルベンゾキノンを製造する方法に関するもので
ある。More specifically, 2,3.6-trimethylphenol is oxidized using phosphorus or silicon as the central element, a heteropolyacid containing molybdenum or tungsten as a catalyst, and hydrogen peroxide as an oxidizing agent to achieve an efficiency of <2,3. 5-)
- It relates to a method for producing lymethylbenzoquinone.
２．３．５−トリメチルベンゾキノンは、合成ビタミン
Ｅ等の原料となる重要な物質で、現在は、２．３．６−
トリメチルフェノールのスルホン化後、二酸化マンガン
酸化による方法で製造されているが、（西独特許第１９
３２３６２号、第２２２５５４３号）、産業廃棄物を副
生じ、しかも製造コストが高価な方法であるため、無公
害且つ安価な製造方法の開発が要望されている。２，３
゜６−トリメチルフェノール、はｍ−クレゾールのオル
トメチル化またはプソイドクメンの酸化により容易に工
業的規模で入手できる。2.3.5-Trimethylbenzoquinone is an important substance that is a raw material for synthetic vitamin E, etc., and currently, 2.3.6-
It is produced by a method of manganese dioxide oxidation after sulfonation of trimethylphenol (West German Patent No. 19).
32362, No. 2225543), these methods generate industrial waste as a by-product and are expensive to manufacture, so there is a demand for the development of a non-polluting and inexpensive manufacturing method. 2,3
6-Trimethylphenol is readily available on an industrial scale by orthomethylation of m-cresol or oxidation of pseudocumene.
さらに、２，３．６−トリメチルフェノールを一段で酸
化して２，３．５−トリメチルベンゾキノンを製造する
方法については、従来数多くの検討がなされており、酸
化剤として、硝酸（特公昭５６−９５１４５号）、過安
息香酸（特公昭５９−３９８４７号）１次亜ハロゲン’
ｖｔ＜特公昭６０−８１１３５号）等を用いる方法が提
案されている。Furthermore, many studies have been conducted on the method of producing 2,3,5-trimethylbenzoquinone by oxidizing 2,3,6-trimethylphenol in one step. 95145), perbenzoic acid (Special Publication No. 59-39847) primary halogen'
A method using VT (Japanese Patent Publication No. 60-81135) has been proposed.
しかしながら、これらの方法でも、有害ガスの発生、高
価な酸化剤の使用、副生成物の生成などの点で問題があ
る。酸化剤として、過酸化水素を使用する製造方法は、
安価な酸化剤であるうえ酸化剤からの副生成物が水のみ
なので、公害防止という観点からも工業的に優れた方法
である。これまで、過酸化水素を酸化剤として２，３．
６−トリメチルフェノールから２．３．５−トリメチル
ベンゾキノンを製造する際、触媒としてルテニウム塩等
の種々の金属塩（Ｃｈｅｍ、Ｌｅｔｔ、、２４．５２４
９ （１９８３）；Ｅｕｒ、Ｐａｔ、Ａｐｐｌ、１０７
１７６）を触媒として用いる方法は公知である。しかし
ながら、かかる従来の方法では、触媒として高価なレア
メタルを使うことや。However, even these methods have problems in terms of generation of harmful gases, use of expensive oxidizing agents, and generation of by-products. The production method uses hydrogen peroxide as an oxidizing agent.
Since it is an inexpensive oxidizing agent and the only by-product from the oxidizing agent is water, it is an industrially excellent method from the viewpoint of pollution prevention. Up until now, hydrogen peroxide has been used as an oxidizing agent in 2, 3.
When producing 2,3,5-trimethylbenzoquinone from 6-trimethylphenol, various metal salts such as ruthenium salts (Chem, Lett, 24.524
9 (1983); Eur, Pat, Appl, 107
176) as a catalyst is known. However, such conventional methods use expensive rare metals as catalysts.
収率が悪いこと等の欠点を有していた。It had drawbacks such as poor yield.
そこで、本発明者は、２，３．６−トリメチルフェノー
ルを過酸化水素で酸化し、２，３．５−トリメチルベン
ゾキノンを製造する際の酸化触媒について鋭意研究を重
ねた結果、安価に市販されているリンまたはケイ素を中
心元素とし、モリブデンまたはタングステンを含むヘテ
ロポリ酸を酸化触媒として使用することにより、高収率
で目的とする２、３．５−トリメチルベンゾキノンを製
造し得ることを見出し、この知見に基づいて本発明をな
すに至った。Therefore, the inventor of the present invention has conducted intensive research on an oxidation catalyst for producing 2,3.5-trimethylbenzoquinone by oxidizing 2,3.6-trimethylphenol with hydrogen peroxide, and has found that it is possible to produce 2,3.5-trimethylbenzoquinone commercially at low cost. We have discovered that the desired 2,3,5-trimethylbenzoquinone can be produced in high yield by using a heteropolyacid containing molybdenum or tungsten as an oxidation catalyst, with phosphorus or silicon as the central element. The present invention was made based on the findings.
すなわち、本発明は、２，３．６−トリメチルフェノー
ルを過酸化水素と反応させて、２，３゜５−トリメチル
ベンゾキノンを製造するにあたり、リンまたはケイ素を
中心元素とし、モリブデンまたはタングステンを含むヘ
テロポリ酸を酸化触媒として使用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方法を提供
するものである。That is, the present invention uses a heteropolymer containing phosphorus or silicon as a central element and containing molybdenum or tungsten in producing 2,3.5-trimethylbenzoquinone by reacting 2,3.6-trimethylphenol with hydrogen peroxide. The present invention provides a method for producing 2,3,5-trimethylbenzoquinone, characterized in that an acid is used as an oxidation catalyst.
本発明は、２，３．６−）−リメチルフェノールとへテ
ロポリ酸と過酸化水素を溶媒中、温和な条件下で単に混
合攪拌するだけで容易に達成され、極めて簡便且つ安全
な酸化方法である。The present invention provides an extremely simple and safe oxidation method that can be easily achieved by simply mixing and stirring 2,3,6-)-limethylphenol, heteropolyacid, and hydrogen peroxide in a solvent under mild conditions. It is.
本発明において、２，３，６−）−リメチルフェノール
を酸化するために酸化剤の過酸化水素水と触媒量のへテ
ロポリ酸が用いられる。過酸化水素水としては、各種濃
度のものが入手できるが、−般に市販されている３０％
から、さらに高濃度の５０〜６０％のものが使用可能で
ある。一方、触かかる酸化剤及び酸化触媒の使用量は、
最適収率に応じ適宜選択すればよいが、通常は前者が反
応に必要な化学量論量の１〜３０倍量、好ましくは２〜
１０倍量が適当であり、後者は２，３．６−トリメチル
フェノールに対して、０．０５モル倍量以下、好ましく
は０．００１〜０．０３モル倍量である。In the present invention, hydrogen peroxide water as an oxidizing agent and a catalytic amount of a heteropolyacid are used to oxidize 2,3,6-)-limethylphenol. Hydrogen peroxide solutions are available in various concentrations, including the commonly available 30%
A higher concentration of 50 to 60% can be used. On the other hand, the amount of oxidizing agent and oxidation catalyst used is
It may be selected as appropriate depending on the optimum yield, but usually the former is 1 to 30 times the stoichiometric amount required for the reaction, preferably 2 to 30 times the stoichiometric amount required for the reaction.
A suitable amount is 10 times, and the latter is not more than 0.05 times, preferably 0.001 to 0.03 times by mole, relative to 2,3.6-trimethylphenol.
本発明の方法において、反応に際して用いられる有機溶
媒としては、酸化剤として過酸化水素水を使用している
ことから、反応を均−系にすることが望ましく、水溶性
の有機溶媒が好ましい。具体例としては、ギ酸、酢酸、
プロピオン酸等の有機酸、アセトニトリル、メタノール
、エタノール、アセトン、Ｎ、Ｎ−ジメチルホルムアミ
ド等が挙げられるが、特に酢酸等の有機酸が望ましい。In the method of the present invention, since hydrogen peroxide is used as an oxidizing agent, it is desirable that the reaction be homogeneous, and water-soluble organic solvents are preferred. Specific examples include formic acid, acetic acid,
Examples include organic acids such as propionic acid, acetonitrile, methanol, ethanol, acetone, N,N-dimethylformamide, etc., and organic acids such as acetic acid are particularly preferred.
本反応における反応温度は、特に厳密な制御を必要とし
ないが、室温付近での反応が好ましく、反応進行と共に
溶液の色は黄色となる。反応終了後、水を加え塩化メチ
レン等、非水溶性有機溶媒で抽出し、硫酸マグネシウム
で乾燥した後、溶媒を留去することにより２，３．５〜
トリメチルベンゾキノンが得られる。このものは公知の
方法によって別途に合成した標品とガスクロマトグラフ
の保持時間の一致、及びＮＭＲスペクトルの−致により
確認した。The reaction temperature in this reaction does not require particularly strict control, but the reaction is preferably around room temperature, and the color of the solution becomes yellow as the reaction progresses. After the reaction is completed, water is added, extracted with a water-insoluble organic solvent such as methylene chloride, dried over magnesium sulfate, and the solvent is distilled off to obtain 2,3.5~
Trimethylbenzoquinone is obtained. This product was confirmed by matching the gas chromatograph retention time with a standard sample separately synthesized by a known method and by matching the NMR spectrum.
本発明方法に従うと、２，３．６−）−リメチルフェノ
ールから２．３．５−トリメチルベンゾキノンを一段階
で、しかも高い収率で得ることができる上に、従来法の
欠陥であった、産業廃棄物を副生ずること、触媒が高価
であること、低収率であること等の欠点が除かれるので
、工業的な２゜３．５−トリメチルベンゾキノンの製造
方法として好適である。According to the method of the present invention, 2,3,5-trimethylbenzoquinone can be obtained from 2,3,6-)-limethylphenol in one step and in a high yield, and it also overcomes the deficiencies of the conventional method. This method is suitable as an industrial method for producing 2.3.5-trimethylbenzoquinone because it eliminates disadvantages such as generation of industrial waste by-products, expensive catalysts, and low yields.
次に本発明を実施例によりさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１〜４
ガラス製フラスコに、２，３．６−トリメチルフェノー
ル２７２■（２ｍｍｏｌ） 、ヘテロポリ酸として下記
のもの１００■を酢酸１０ｍ１に溶かし、６０％過酸化
水素水を２ｍ１滴下した。窒素雰囲気下、温度を３０℃
に保ちながら５時間攪拌を続けた。反応終了後、水を５
０ｍ１加え、２０ｍ１の塩化メチレンで３回抽出した。Examples 1 to 4 In a glass flask, 272 µ (2 mmol) of 2,3.6-trimethylphenol and 100 µ of the following heteropolyacid were dissolved in 10 ml of acetic acid, and 2 ml of 60% hydrogen peroxide solution was added dropwise. Temperature: 30℃ under nitrogen atmosphere
Stirring was continued for 5 hours while maintaining the temperature. After the reaction is complete, add 5 liters of water.
0 ml was added and extracted three times with 20 ml of methylene chloride.
抽出液を硫酸マグネシウムで乾燥後、生成した２、３．
５−トリメチルベンゾキノンの量をガスクロマトグラフ
により分析した。After drying the extract with magnesium sulfate, the products 2, 3.
The amount of 5-trimethylbenzoquinone was analyzed by gas chromatography.
実１例 へテロポリ酸 反応率（
％） ＠寧（％） 選択率（％）１ リ
ンモリブデン１ ９９，９ ７８．３
７８．３２ ケイモリブデン！
９６，２ ６６．６ ６９．２３
リンタングステンｌ ９３．７
６３．２ ６７．５濃度を３０％に変え、反
応時間を１２時間にしたところ次のような結果が得られ
た。Actual example: Heteropolyacid reaction rate (
%) @Ning (%) Selectivity (%) 1 Phosphormolybdenum 1 99.9 78.3
78.32 Kei Molybdenum!
96.2 66.6 69.23
Phosphor tungsten l 93.7
63.2 When the 67.5 concentration was changed to 30% and the reaction time was changed to 12 hours, the following results were obtained.
実ＩＡ＠ ヘテロポリ酸 反応
率（幻 収率（％） ！火車（％）５
リンモリブデンｌ ９９．９ ６０
．９ ６０．９６ ケイモリブデンｌ
９９．９ ６６．７ ６６．７
７ ワンタングステンＩ ９４．
６ ５６，６ ５９．８８ ケイ
タングステンＩ ９６．６ ６６．０
６８．４実施例９〜１２
実施例５〜８において、反応時間を５時間としたところ
次のような結果が得られた６
実施例 へテロポリ酸 反応率（
％） 収車（％） ！火車（％）９ リンモ
リブデン！１ ７９，４ ６１．５
７７．５１０ ケイモリブデンＩ
５９．２ ５９．２ １００．０１１
リンタングステンｌ ６０．８ ４
３，５ ７１．５１２ ケイタングステンｌ
４４．６ ４４．６ １００．０比
較例１
実施例１において、触媒としてのリンモリブデン酸を用
いないで行ったところ次のような結果が得られた。Real IA @ heteropolyacid reaction rate (phantom yield (%)! Kasha (%) 5
Phosphormolybdenum l 99.9 60
．． 9 60.96 Keimolybdenum l
99.9 66.7 66.7
7 One Tungsten I 94.
6 56,6 59.88 Silicon Tungsten I 96.6 66.0
68.4 Examples 9 to 12 In Examples 5 to 8, when the reaction time was set to 5 hours, the following results were obtained. 6 Example Heteropolyacid Reaction rate (
%) Collection of vehicles (%)! Kasha (%) 9 Phosphorus molybdenum! 1 79, 4 61.5
77.510 Keimolybdenum I
59.2 59.2 100.011
Phosphor tungsten l 60.8 4
3,5 71.512 Silicon tungsten l
44.6 44.6 100.0 Comparative Example 1 When Example 1 was carried out without using phosphomolybdic acid as a catalyst, the following results were obtained.
反応率（％）収率（％）選択率（％）
比較例２
実施例９において、リンモリブデン酸の代わりにオルト
モリブデン酸−水塩（７，２■、０．０４ ＋ｏｍｏｌ
）を用いて反応を行ったところ次のような結果が得られ
た。Reaction rate (%) Yield (%) Selectivity (%) Comparative example 2 In Example 9, orthomolybdic acid hydrate (7,2■, 0.04 + omol
), the following results were obtained.
反応率（％） 収率（％）選択率（％）比較例３
実施例９において、リンモリブデン酸の代わりにオルト
タングステン酸（１０ｍｇ＋０．０４ｍｍｏｌ）を用い
て反応を行ったところ次のような結果が得られた。Reaction rate (%) Yield (%) Selectivity (%) Comparative example 3 In Example 9, when the reaction was carried out using orthotungstic acid (10 mg + 0.04 mmol) instead of phosphomolybdic acid, the following results were obtained. was gotten.
反応率（％）収率（％）選択率（％） ６５．１ ２１．１ ３２．４Reaction rate (%) Yield (%) Selectivity (%) 65.1 21.1 32.4
Claims (1)
２，３，５−トリメチルベンゾキノンを製造するにあた
り、酸化剤として過酸化水素、酸化触媒としてリンまた
はケイ素を中心元素とし、モリブデンまたはタングステ
ンを含むヘテロポリ酸を使用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方法。(1) Oxidize 2,3,6-trimethylphenol,
In producing 2,3,5-trimethylbenzoquinone, hydrogen peroxide is used as an oxidizing agent, and a heteropolyacid containing molybdenum or tungsten is used as an oxidation catalyst, with phosphorus or silicon as the central element.
Method for producing 3,5-trimethylbenzoquinone.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63062878A JPH01238552A (en) | 1988-03-16 | 1988-03-16 | Production of 2,3,5-trimethylbenzoquinone |
| EP89302025A EP0338666B1 (en) | 1988-03-16 | 1989-03-01 | Method for the preparation of 2,3,5-trimethylbenzoquinone |
| DE8989302025T DE68901576D1 (en) | 1988-03-16 | 1989-03-01 | METHOD FOR PRODUCING 2,3,5-TRIMETHYLBENZOCHINONE. |
| US07/318,716 US5245059A (en) | 1988-03-16 | 1989-03-03 | Method for the preparation of 2,3,5-trimethylbenzoquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63062878A JPH01238552A (en) | 1988-03-16 | 1988-03-16 | Production of 2,3,5-trimethylbenzoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01238552A true JPH01238552A (en) | 1989-09-22 |
| JPH0529379B2 JPH0529379B2 (en) | 1993-04-30 |
Family
ID=13212964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63062878A Granted JPH01238552A (en) | 1988-03-16 | 1988-03-16 | Production of 2,3,5-trimethylbenzoquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01238552A (en) |
-
1988
- 1988-03-16 JP JP63062878A patent/JPH01238552A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0529379B2 (en) | 1993-04-30 |
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