JPH02209841A - Production of 2,3,5-trimethybenzoquinone - Google Patents
Production of 2,3,5-trimethybenzoquinoneInfo
- Publication number
- JPH02209841A JPH02209841A JP2972089A JP2972089A JPH02209841A JP H02209841 A JPH02209841 A JP H02209841A JP 2972089 A JP2972089 A JP 2972089A JP 2972089 A JP2972089 A JP 2972089A JP H02209841 A JPH02209841 A JP H02209841A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- catalyst
- reaction
- compound
- copper chloride
- 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 description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 5
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims abstract 6
- 238000000034 method Methods 0.000 claims description 12
- 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 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 6
- 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 abstract description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229930003427 Vitamin E Natural products 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 abstract description 2
- 229940046009 vitamin E Drugs 0.000 abstract description 2
- 235000019165 vitamin E Nutrition 0.000 abstract description 2
- 239000011709 vitamin E Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 for example Substances 0.000 description 3
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical class [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- 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、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、 ５．５− ）リメチルペンゾキノンの製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 2,5,5-)limethylpenzoquinone, which is useful as a synthetic intermediate for pharmaceuticals such as vitamin E.
２、３．５−）リメチルベンゾキノンの製造方法として
は、２．３．６− ）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。As a method for producing 2,3.5-)limethylbenzoquinone, 2.3.6-)limethylphenol (2゜3.6
-TMP) with an inorganic oxidizing agent, or with oxygen in the presence of a catalyst.
Ｉｃ制
前者の無機へを用いる方法では、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
な用いる方法では、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、
又ノ・ロゲン化鋼及びノ・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５５−１７５８５
号、特開昭５９−２２５１！１号、特開昭６３−２８０
０４０号で代表される方法では、触媒を２，３゜６−Ｔ
ＭＰ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。In the former method using inorganic substances, for example, potassium permanganate, manganese dioxide, lead oxide, etc. are used as oxidizing agents, and the amount thereof is required to be more than the stoichiometric amount, and metal salts in a low valence state are used. processing is required. In addition, in the latter method of oxidation in the presence of a catalyst, for example, a method in which a cobalt complex is used as a catalyst, the catalytic activity is high at the initial stage of the reaction, but the life of the catalyst is extremely short, making it difficult to use industrially. Further, copper halide is used as a catalyst. Method,
In addition, although the method using non-logogenated steel and non-logogenated lithium can maintain high reaction rate and selectivity, it has various drawbacks that need to be solved. For example, Tokuko Sho 55-17585
No., JP-A-59-2251!1, JP-A-63-280
In the method typified by No. 040, the catalyst is 2,3°6-T.
If the same weight or more than MP is used, the yield will be low and the reaction rate will be low.
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で用いること、■使用量が
少ないこと、■生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。In order to establish a method that is more suitable for industrial implementation and solves the drawbacks of the known techniques mentioned above, the present inventor aims to: (1) use a commercially available general reagent without using an expensive special catalyst, and (2) use a small amount. The present invention was completed by discovering that the object could be achieved by using a production method.
本発明の要旨とするところは、２．３．６−ＴＭＰを、
触媒として、塩化鋼及びバナジウム化合物の存在下にお
いて、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を製造するところ
にある。The gist of the present invention is that 2.3.6-TMP is
Oxidized with oxygen or oxygen-containing gas in a solvent in the presence of chlorinated steel and a vanadium compound as a catalyst,
．． 3.5-Trimethylbenzoquinone is produced.
本発明方法での２．３．６− Ｔ Ｍ Ｐの濃度は、反
応液に対して５〜５０重量％重景で、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
不活性ガスで稀釈したガスで、空気の使用が最も経済的
である。The concentration of 2.3.6-TMP in the method of the present invention is 5 to 50% by weight relative to the reaction solution, and if the concentration is set too high, precipitation of quinones during the reaction will increase; Operability deteriorates. The gas used for the oxidation reaction is oxygen or a gas obtained by diluting oxygen with an inert gas, and air is most economically used.
反応に使用する溶媒としては、下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
Ｒ＋ＯＣＲ，ＣＨ，＋ＯＲ’
ｎ：１〜４
Ｒ： ＣＨｓ 、Ｃ２Ｈｓ 、Ｃ３Ｈ７、Ｃ４Ｈ０Ｒ’
： Ｈ，ＣＨｓ 、Ｃ２Ｈ５、Ｃ３Ｈ？ 、Ｃ４ＨＱ
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、インプロピ
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。又ノ・ロゲン化炭化水素、芳香族
炭化水素１．アルキルアルコール等が所望により、溶媒
の全体として又は構成成分として使用できる。As the solvent used for the reaction, polyethylene glycol alkyl ethers represented by the following general formula R+OCR, CH, +OR' n: 1-4 R: CHs, C2Hs, C3H7, C4H0R'
: H, CHs, C2H5, C3H? , C4HQ
Acid amides such as dimethylformamide (DMF) and dimethylacetamide (DMA); Ketones such as acetone and methyl isobutyl ketone; cyclic ethers such as dioxane and tetrahydrofuran; chain ethers such as butyl ether and inpropyl ether; acetonitrile, etc. Nitriles; There are others. Also, logogenated hydrocarbons, aromatic hydrocarbons 1. Alkyl alcohols and the like can be used as a whole or as a component of the solvent, if desired.
本発明の溶媒として特に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、ＤＭＦ。Particularly recommended solvents for the present invention include ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, and DMF.
ＤＭＡ、アセトン等があり、これらは収率の向上に効果
的に寄与する。There are DMA, acetone, etc., and these effectively contribute to improving the yield.
尚、溶媒中の水分は、反応に好ましい結果をもたらすと
は限らず反応で生成する水も反応の進行と共に溜去する
ことが望まれる。Note that water in the solvent does not necessarily bring about favorable results in the reaction, and it is desirable that the water produced in the reaction be distilled off as the reaction progresses.
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。又バナ
ジウム化合物としては、バナジウムの酸化物、ノ・ロゲ
ン化物、酸素酸塩、錯化合物から適当に選択されるが、
具体的には、Ｖ２Ｏ，、ＶＣＣｌ、、ＶＯＣｔ、、ＭＶ
Ｏ３（Ｍ：ＮＨ４，Ｎａ、Ｋ、 Ｌｉ 入に４ （：Ｖ
（ＣＮ）６１３Ｈ２０、Ｋ、 Ｉ：Ｖ（ＣＮ）６ ）が
あり、特にメタバナジン酸のアルカリ金属塩、アンモニ
ウム塩が望ましい。Copper chloride used as a catalyst includes cuprous chloride and cupric chloride, with cupric chloride being particularly preferred. In addition, the vanadium compound is appropriately selected from vanadium oxides, chloride compounds, oxyacid salts, and complex compounds.
Specifically, V2O,,VCCl,,VOCt,,MV
O3 (M: NH4, Na, K, Li 4 (:V
(CN)613H20, K, I:V(CN)6), and alkali metal salts and ammonium salts of metavanadate are particularly desirable.
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− Ｔ Ｍ Ｐ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。一方、バナ
ジウム化合物は、０．００１〜５倍モル好ましくは、０
．０１〜１．０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 per 2.3.6-TMP used.
~10 times the mole, preferably 0.05 to 5 times the mole, more preferably 0.1 to 0.5 times the mole. On the other hand, the vanadium compound is preferably 0.001 to 5 times the mole
．． 01 to 1.0 times the molar amount is used.
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 when air is used, it is preferable to slightly increase the pressure in order to increase the reaction rate.
反応温度は、２０℃乃至１００℃、好ましくは、５０乃
至８０℃。反応時間は１乃至１０時間。The reaction temperature is 20°C to 100°C, preferably 50 to 80°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。Note that these pressure, temperature, and time can be easily selected within the range of conventional technology.
本発明方法による酸化反応生成液からの２，６゜６−ト
リメチルベンゾキノンの分離は、例ｔば、反応液を水層
と分液し、有機層を水洗後蒸上により分離子ることがで
きる。The separation of 2,6゜6-trimethylbenzoquinone from the oxidation reaction product liquid by the method of the present invention can be carried out, for example, by separating the reaction liquid into an aqueous layer, washing the organic layer with water, and then separating it by vaporization. .
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 shown together with comparative examples in order to demonstrate the effects of the present invention.
実施例１〜４
３００ｍ１四つロフラスコ中に塩化銅２水和物１７５’
（０，１モル）、メタバナジン酸アンモン１．２ Ｐ、
（０，０１モル）、蒸留水１０ｒｌＬｌ、表−１の有機
溶媒５Ｑｍｌを入れ加温し６０℃に保ち、約７０Ｏｒｐ
ｍで攪拌を行ないながら酸素ガスを流速２００ｍ１／１
ｒｉｓで液面下に通気し同有機溶媒５０ｍ１に２．５．
６−ＴＭＰ３４ｔＣ０，２５モＡ／）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２，５．６−Ｔ
ＭＰが消失する迄反応を行ない、終了後適当量の水を加
えトルエンで抽出を行ないガスクロマトグラフによる分
析を行なった。Examples 1-4 Copper chloride dihydrate 175' in a 300 m 1 four-loaf flask
(0.1 mol), ammonium metavanadate 1.2 P,
(0.01 mol), 10 rlLl of distilled water, and 5 Qml of the organic solvent shown in Table 1 were heated and kept at 60°C.
Flow rate of oxygen gas is 200m1/1 while stirring at m
2.5.
A solution of 6-TMP34tC0,25 moA/) was added dropwise over a period of 2 hours, and after the dropwise addition, 2,5.6-T
The reaction was carried out until MP disappeared, and after completion of the reaction, an appropriate amount of water was added, extraction was performed with toluene, and analysis was performed by gas chromatography.
表−１
実施例５〜８
３００ｄ四ツロフラスコ中に塩化銅２水和物１７ｆＰ（
０，１モル）、メタバナジン酸アンモ１．２Ｐ（０，０
１モル）、表−２の有機溶媒５０ｍ／を入れ加温し６０
℃に保ち、約７０Ｏｒｐｍで攪拌を行ないながら酸素ガ
スを流速２００ｍ／／―で液面下に通気し同有機溶媒５
０ｍ１に２．６゜６−ＴＭＰ ３４５４（０，２５モル
）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実施例
１〜４と同様な処理゛の後分析を行なった。Table-1 Examples 5 to 8 Copper chloride dihydrate 17fP (
0.1 mol), ammo metavanadate 1.2P (0.0
1 mol) and 50 m/ml of the organic solvent shown in Table 2 were added and heated to 60 m
℃, and while stirring at about 70 rpm, oxygen gas was bubbled under the liquid surface at a flow rate of 200 m//- to dissolve the organic solvent 5.
Example 1 A solution of 2.6゜6-TMP 3454 (0.25 mol) dissolved in 0ml was added dropwise over a period of 2 hours, and after the dropwise addition was completed, the reaction was continued until the 2.3.6-TMP disappeared. Analysis was performed after the same treatment as in ~4.
表−２
注；ＴＭＢＱ ： ２，５．− トリメチルベンゾキノ
ン比較例１〜４
実施例１〜４においてメタバナジン酸アンモを加えない
で反応を行なったところ次の結果を得た。Table-2 Note: TMBQ: 2,5. - Trimethylbenzoquinone Comparative Examples 1 to 4 When the reactions in Examples 1 to 4 were carried out without adding ammo metavanadate, the following results were obtained.
表−６
手続補正書（自発）
平成１年４月ノθ日
特許庁長官 吉 １）文 毅 殿
１、事件の表示
平成１年特願第２９７２０号
２、発明の名称
２、３．５−トリメチルベンゾキノンの製造方法実施例
５〜８についても行なった結果を下記に示す。Table-6 Procedural amendment (voluntary) April 1st, 1999 Director General of the Japan Patent Office Yoshi 1) Moon Takeshi 1, Indication of the case 1999 Patent Application No. 29720 2, Name of the invention 2, 3.5- The results of Examples 5 to 8 of the method for producing trimethylbenzoquinone are shown below.
表−４Table-4
Claims (1)
塩化鋼及びバナジウム化合物の存在下において、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方法。Production of 2,3,5-trimethylbenzoquinone, characterized in that 1,2,3,6-trimethylphenol is oxidized with oxygen or an oxygen-containing gas in a solvent in the presence of chlorinated steel and a vanadium compound as a catalyst. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1029720A JP2592324B2 (en) | 1989-02-10 | 1989-02-10 | Method for producing 2,3,5-trimethylbenzoquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1029720A JP2592324B2 (en) | 1989-02-10 | 1989-02-10 | Method for producing 2,3,5-trimethylbenzoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02209841A true JPH02209841A (en) | 1990-08-21 |
| JP2592324B2 JP2592324B2 (en) | 1997-03-19 |
Family
ID=12283944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1029720A Expired - Lifetime JP2592324B2 (en) | 1989-02-10 | 1989-02-10 | Method for producing 2,3,5-trimethylbenzoquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2592324B2 (en) |
-
1989
- 1989-02-10 JP JP1029720A patent/JP2592324B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2592324B2 (en) | 1997-03-19 |
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