JPS601292B2 - Synthesis method of dihydrocoenzyme Q compounds - Google Patents
Synthesis method of dihydrocoenzyme Q compoundsInfo
- Publication number
- JPS601292B2 JPS601292B2 JP50113727A JP11372775A JPS601292B2 JP S601292 B2 JPS601292 B2 JP S601292B2 JP 50113727 A JP50113727 A JP 50113727A JP 11372775 A JP11372775 A JP 11372775A JP S601292 B2 JPS601292 B2 JP S601292B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- methyl
- tables
- formulas
- dimethoxy
- 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
Description
【発明の詳細な説明】
本発明は次の一般式（１）
〔式中Ｒは次式
の基を表わし、ｎは０〜９の整数を、Ａ，Ｂは水素原子
あるいは場合によりＡ−Ｂで結合手を形成する事を表わ
す。Detailed Description of the Invention The present invention is based on the following general formula (1) [wherein R represents a group of the following formula, n is an integer of 0 to 9, and A and B are hydrogen atoms or, in some cases, A-B represents the formation of a bond.
〕で表わされる２，３−ジメトキシー５−置換−６ーメ
チルーベンゾ／・ィドロキノンの新規な合成法に関する
ものである。This invention relates to a novel method for synthesizing 2,3-dimethoxy5-substituted-6-methyl-benzo/hydroquinone represented by the following formula.
化合物（１）を例えば袴公昭３９一１７５１４号の方法
に従って酸化して得られる次の一般式（０）〔式中Ｒは
前記の意味を表わす〕で表わされる化合物は補酵素Ｑと
して知られ、特にＡ−Ｂが結合手を形成し、ｎが９であ
る２，３ージメトキシー５ーメチルー６−デカプレニル
−１，４ーベンゾキノン〔２，３−ジメトキシー５ーメ
チル−６一（３，７，１１，１５，１９，２３，２７，
３１，３５，３９−デカメチルテトラコンタデカエン−
２，６，１０，１４，１８，２２，２６，３０，３４，
３８−イール）−１，４−ペンゾキノン〕は補酵素Ｑ，
ｏと称せられるもので、生体内において電子伝達系に関
与すると共にエネルギー産生に重要な役割を果し、虚血
による心筋組織の病変の改善、低下した心拍出量の増加
、アルドステロンのＮａ貯留作用に対する桔抗作用等を
有し、うっ血陣０不全、肺うっ血、．肝腫張および狭心
症の予防および治療に有効である。A compound represented by the following general formula (0) [wherein R represents the above-mentioned meaning] obtained by oxidizing compound (1), for example, according to the method of Hakama Kosho No. 39-117514, is known as coenzyme Q, In particular, 2,3-dimethoxy5-methyl-6-decaprenyl-1,4-benzoquinone [2,3-dimethoxy5-methyl-6-(3,7,11,15, 19, 23, 27,
31,35,39-decamethyltetracontadecaene-
2, 6, 10, 14, 18, 22, 26, 30, 34,
38-yl)-1,4-penzoquinone] is coenzyme Q,
It is involved in the electron transport system in vivo and plays an important role in energy production, improving myocardial tissue lesions caused by ischemia, increasing decreased cardiac output, and Na retention in aldosterone. It has an anti-inflammatory effect, causing congestion, pulmonary congestion, etc. It is effective in preventing and treating liver swelling and angina pectoris.
化合物（１）の合成法としては、２，３ージメトキシー
６ーメチルー１，４−ペンゾハイドロキノンまたはその
１ーモノアシレートと（イソ）デカブレノールまたはそ
の反応性叢導体とをギ酸、硫酸、塩酸、燐酸、ｐ−トル
ェンスルホン酸等のプロトン酸；塩化亜鉛、塩化アルミ
ニウム、三弗化ホウ素エーテル錆体等のルイス酸あるい
はこれらの混合物等の酸性縮合触媒の存在下に反応させ
て得る方法が知られている（特公昭３９一１７５１３号
、同４６一３９６７号参照）。As a method for synthesizing compound (1), 2,3-dimethoxy6-methyl-1,4-penzohydroquinone or its 1-monoacylate and (iso)decabrenol or its reactive conductor are mixed with formic acid, sulfuric acid, hydrochloric acid, phosphoric acid, p- A known method is to react in the presence of an acidic condensation catalyst such as a protonic acid such as toluenesulfonic acid; a Lewis acid such as zinc chloride, aluminum chloride, boron trifluoride ether rust, or a mixture thereof ( (See Special Publications No. 39-17513 and No. 46-3967).
しかしこれらの方法は、縮合工程の収率が良くないため
、目的とするキノン化合物の収率は粗生成物でも高々３
０％と非常に低い。However, in these methods, the yield of the condensation step is not good, so the yield of the target quinone compound is only 3 at most even for the crude product.
Very low at 0%.
さらに使用する駿触媒は何れも腐蝕性が強く装置上好ま
しくないのみならず、溶出した金属が生成物を汚染し工
業的に実施するに際し、その不利は免れない。また前記
触媒を使用することによって、得られた反応生成物から
目的生成物を分離するにあたって、中和、抽出等の操作
を要し、更に原料に対して多量の触媒を使用し、その上
それらは反応後に廃棄しなければならない場合が多く、
コスト上並びに公害上の見地から好ましくないなど、工
業的に多くの難点を有している。本発明者等は化学式（
ロ）で表わされるキノン化合物を効率よく得る方法の開
発を目的として前駆物質であるハイドロキノン化合物を
効率よく、しかも工業的に有利に得るための縮合工程改
善の探索に努力し、本発明の方法に到達した。Furthermore, all of the Shun catalysts used are highly corrosive and are not only undesirable in terms of equipment, but also the eluted metal contaminates the product, which is an unavoidable disadvantage when used industrially. Furthermore, by using the above-mentioned catalyst, operations such as neutralization and extraction are required to separate the desired product from the resulting reaction product, and a large amount of catalyst is used relative to the raw material, and in addition, often have to be discarded after the reaction;
It has many industrial disadvantages, such as being undesirable from the viewpoint of cost and pollution. The inventors have determined that the chemical formula (
With the aim of developing a method for efficiently obtaining the quinone compound represented by b), efforts have been made to search for improvements in the condensation process to obtain the precursor hydroquinone compound efficiently and industrially advantageously, and the method of the present invention has been developed. Reached.
本発明の方法は次の化学式（血）
で表わされる２，３ージメトキシ−５ーメチルーベンゾ
ノ・ィドロキノンと次の一般式（Ｗ）又はそのイソ体〔
式中Ｒは前記の意味を表わす。The method of the present invention consists of 2,3-dimethoxy-5-methyl-benzonohydroquinone represented by the following chemical formula (blood) and the following general formula (W) or its isoform [
In the formula, R represents the above meaning.
〕で表わされる（ィソ）プレノールまたはその反応性誘
導体を反応せしめて次の一般式（１）〔式中Ｒは前記の
意味を表わす。] (iso)prenol or its reactive derivative is reacted to form the following general formula (1) [wherein R represents the above meaning.
〕で表わされる２，３−ジメトキシー５−鷹換−６−メ
チル−ペンゾノ・ィドロキノンを合成するに際して、反
応触媒としてシリカアルミナ系化合物を用いるものであ
る。A silica-alumina compound is used as a reaction catalyst in synthesizing 2,3-dimethoxy-5-takaki-6-methyl-penzonohydroquinone represented by the following formula.
本発明において使用される（ィソ）プレノール（Ｗ）ま
たはその反応性誘導体としては、例えば３−メチルブテ
ン−２−オール一１、３ーメチルブテンー１−オール−
３、ゲラニオール、リナロール、ネロール、ネロリドー
ル、フイトール、イソフイ‐トール、ゲラニルゲラニオ
ール、ゲラニルリナロール、ゲラニルフアルネソール、
ゲラニルネロリドール、フアルネンルフアルネソール、
フアルネシルネロリドール、ゲラニルゲラニルフアルネ
ソール、ソラネソール、デカプレノール、イソデカプレ
ノールあるいはそれらアルコール体から導かれるハラィ
ド体をあげる事ができる。The (iso)prenol (W) or its reactive derivative used in the present invention includes, for example, 3-methylbuten-2-ol-1,3-methylbuten-1-ol-
3. Geraniol, linalool, nerol, nerolidol, phytol, isophytol, geranylgeraniol, geranyl linalool, geranyl pharnesol,
Geranyl nerolidol, falnenruf arnesol,
Examples include farnesyl nerolidol, geranylgeranyl farnesol, solanesol, decaprenol, isodecaprenol, and halides derived from these alcohols.
本発明において反応触媒として使用するシリカアルミナ
系化合物としては、例えば白土、活性白土、カオリン、
天然および合成ゼオラィト、シリカアルミナ、シリカア
ルミナボリア、シリカアルミナマグネシア等を挙げる事
ができる。本発明の方法を行なうに際してはベンゼン、
トルェン、キシレン等の芳香族炭化水素系溶媒；エチル
ェーナル、イソフ。ロピルエーテル、テトラノ・イドロ
フラン等のエーテル系溶媒；ペンタン、ヘキサン「ヘプ
タン、オクタン、イソオクタン、石油ェー７ル、リグロ
ィン等の脂肪族炭化水素系溶媒；酢酸エチルェステル等
のェステル系溶媒等を適宜選択して使用するのが好まし
い。本発明の方法を実施する事により、化合物（１）の
収率が大きく向上し、例えば２，３ージメトキシ−５−
デカプレニルー６ーメチルー１，４−ペンゾハイドロキ
ノン（ハイドロコエンザイムＱ，ｏ）では収率６５％に
達した。Examples of the silica-alumina compounds used as reaction catalysts in the present invention include clay, activated clay, kaolin,
Natural and synthetic zeolites, silica alumina, silica alumina boria, silica alumina magnesia, etc. may be mentioned. When carrying out the method of the present invention, benzene,
Aromatic hydrocarbon solvents such as toluene and xylene; ethylenal and isof. Ether solvents such as lopylether and tetranohydrofuran; pentane, hexane; aliphatic hydrocarbon solvents such as heptane, octane, isooctane, petroleum ether, and ligroin; and ester solvents such as ethyl acetate. By carrying out the method of the present invention, the yield of compound (1) is greatly improved, for example, 2,3-dimethoxy-5-
The yield of decaprenyl-6-methyl-1,4-penzohydroquinone (hydrocoenzyme Q,o) reached 65%.
また従来法の如く酸性縮合剤を使用しないため、装置を
腐蝕することもなく、また目的物を汚染する事もない。
本発明を実施する方法としては連続式あるいは回分式の
いずれをも採用する事ができる。連続式で行なう場合に
は、例えばシリカアルミナ系化合物を反応塔に充填し、
これに化合物（ｍ）および（Ｗ）またはその反応性誘導
体を本発明において使用する溶媒に溶解して得た溶液を
順次または同時に通過させる事により実施する事ができ
る。回分式で行なう場合には、例えば反応器にシリカア
ルミナ系化合物を入れ、これに化合物（ｍ）および（Ｗ
）またはその反応性誘導体を本発明に使用する溶媒に溶
解して得た溶液を加え、損拝する事によって実施するこ
とができる。以上より本発明は化合物（１）を収率上、
操作上、工業的に有利に得る方法を提供するものである
。Furthermore, unlike conventional methods, no acidic condensing agent is used, so there is no corrosion of the equipment or contamination of the target object.
As a method for implementing the present invention, either a continuous method or a batch method can be adopted. In the case of continuous operation, for example, a silica-alumina compound is packed into a reaction column,
This can be carried out by sequentially or simultaneously passing through this a solution obtained by dissolving compounds (m) and (W) or their reactive derivatives in the solvent used in the present invention. When carrying out batchwise, for example, a silica alumina compound is placed in a reactor, and the compound (m) and (W) are added to the reactor.
) or a reactive derivative thereof in the solvent used in the present invention, and then add a solution obtained by dissolving the same in the solvent used in the present invention. From the above, the present invention provides compound (1) in higher yield,
This provides an operationally and industrially advantageous method.
なお化合物（１）は不安定な物質であるので反応混合物
から単離することなく直ちに公知の方法で酸化して化合
物（０）として取るのが好ましい。Since compound (1) is an unstable substance, it is preferable to immediately oxidize it by a known method to obtain compound (0) without isolating it from the reaction mixture.
次に実施例により本発明を説明する。Next, the present invention will be explained with reference to examples.
実施例 １
２，３−ジメトキシ−５ーデカプレニルー６−メチルー
ベンゾキノン（ＣｏＱ，ｏ）の合成２，３ージメトキシ
ー５ーメチルーベンゾハイドロキノン１１夕をベンゼン
２０の‘に溶解し、シリカアルミナ２０夕を加え、更に
ｎーヘキサン３０の‘を滴下したのち、この溶液にデカ
プレノール１４夕をｎーヘキサン１０奴に溶解して加え
た。Example 1 Synthesis of 2,3-dimethoxy-5-decaprenyl-6-methyl-benzoquinone (CoQ,o) 11 parts of 2,3-dimethoxy-5-methyl-benzohydroquinone was dissolved in 20 parts of benzene, and 20 parts of silica alumina was added. Further, 30 parts of n-hexane was added dropwise, and 14 parts of decaprenol dissolved in 10 parts of n-hexane was added to this solution.
この溶液を２時間加熱還流した。反応混合物を炉過し、
炉過物をエチルエーテルで洗い、洗液は炉液と合し、水
、５％苛性ソーダ水溶液、水で順次梁総したのち酢酸５
地、二酸化鉛７夕および活性炭１夕を加え蝿伴下、室温
にて１時間保ち炉過した。炉液は水洗し三硝で乾燥した
のち濃縮、油状残澄１６．２夕を得た。この油状残澄を
シリカゲルクロマトにより精製した（シリカゲル３００
夕，溶出溶媒：エーテル・ｎ−ヘキサン混液）。淡黄色
油状物質１１．２夕を得た。収率６５．０％（使用した
デカプレノール純度９４．４％より換算）この淡黄色油
状物質をアセトン１５０地に溶解し一夜０℃に保ち、燈
黄色結果９．１夕を得た。This solution was heated to reflux for 2 hours. filtering the reaction mixture;
The filtrate was washed with ethyl ether, and the washing liquid was combined with the furnace liquid, and washed with water, 5% caustic soda aqueous solution, and water in order, and then washed with acetic acid.
After adding lead dioxide for 7 days and activated carbon for 1 day, the mixture was kept at room temperature for 1 hour in the presence of flies and filtered. The furnace solution was washed with water, dried with trisnitrogen, and concentrated to obtain an oily residue of 16.2 mm. This oily residue was purified by silica gel chromatography (silica gel 300
Elution solvent: ether/n-hexane mixture). 11.2 hours of pale yellow oil was obtained. Yield: 65.0% (calculated from the purity of decaprenol used, 94.4%) This pale yellow oily substance was dissolved in acetone 150 and kept at 0°C overnight to give a light yellow color of 9.1%.
融点４９〜５００○本品のＵＶ，ＩＲ．ＮＭＲおよびＭ
ＡＳスペクトル測定値は標品とよく同定した。Melting point: 49-500○UV, IR. of this product. NMR and M
The AS spectrum measurements were well identified with the standard.
実施例 ２
２，３ージメトキシー５−フイチルー６−メチル−１，
４−ペンゾキノンの合成。Example 2 2,3-dimethoxy-5-phytyl-6-methyl-1,
Synthesis of 4-penzoquinone.
２，３−ジメトキシ−５−メチル−ペンゾハイドロキノ
ン２２．５夕，ィソフィトール１３，３夕を実施例１に
従って反応処理した。2,3-Dimethoxy-5-methyl-penzohydroquinone 22.5 hours and isophytol 13.3 hours were reacted according to Example 1.
赤色油状物２６．４夕を得た。収率９４．０％（使用し
たィソフィトール純度９０．０％より換算）本品のＵＶ
，ＩＲ，ＮＭＲおよびＭＡＳスペクトル測定値は標品と
よく同定した。26.4 hours of a red oil was obtained. Yield: 94.0% (calculated from the purity of isophytol used: 90.0%) UV of this product
, IR, NMR and MAS spectra measurements were well identified with the standard.
Claims (1)
ハイドロキノンと次の一般式▲数式、化学式、表等があ
ります▼ 又はそのイソ体 ▲数式、化学式、表等があります▼ 〔式中Ｒは次式 ▲数式、化学式、表等があります▼ の基を表わし、ｎは０〜９の整数を、Ａ，Ｂは水素原子
あるいは場合によりＡ−Ｂで結合手を形成する事を表わ
す。 〕で表わされる（イソ）プレノールまたはその反応性誘
導体を反応せしめて次の一般式▲数式、化学式、表等が
あります▼ 〔式中Ｒは前記の意味を表わす〕 で表わされる２，３−ジメトキシ−５−置換−６−メチ
ル−ベンゾハイドロキノンを合成するに際して、反応触
媒としてシリカアルミナ系化合物を用いる事を特徴とす
る、２，３−ジメトキシ−５−置換−６−メチル−ベン
ゾハイドロキノンの合成法２ 次の化学式 ▲数式、化学式、表等があります▼ で表わされる２，３−ジメトキシ−５−メチル−ベンゾ
ハイドロキノンと次の一般式▲数式、化学式、表等があ
ります▼ 又はそのイソ体 ▲数式、化学式、表等があります▼ 〔式中Ｒは次式 ▲数式、化学式、表等があります▼ の基を表わし、ｎは０〜９の整数を、Ａ，Ｂは水素原子
あるいは場合によりＡ−Ｂで結合手を形成する事を表わ
す。 〕で表わされる（イソ）プレノールまたはその反応性誘
導体を反応せしめて次の一般式▲数式、化学式、表等が
あります▼ 〔式中Ｒは前記の意味を表わす〕 で表わされる２，３−ジメトキシ−５−置換−６−メチ
ル−ベンゾハイドロキノンを合成するに際して、反応触
媒としてシリカアルミナ系化合物を用い、得た２，３−
ジメトキシ−５−置換−６−メチル−ベンゾハイドロキ
ノンを酸化剤で処理する事を特徴とする、次式▲数式、
化学式、表等があります▼ 〔式中Ｒは前記の意味を表わす〕 で表わされる２，３−ジメトキシ−５−置換−６−メチ
ル−１，４−ベンゾキノンの合成。[Claims] 1. 2,3-dimethoxy-5-methyl-benzohydroquinone represented by the following chemical formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or its isoform▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents the group of the following formula▲There are mathematical formulas, chemical formulas, tables, etc.▼, where n is an integer from 0 to 9, and A and B are hydrogen. Indicates that atoms or, in some cases, A-B form a bond. ] (iso)prenol or its reactive derivative is reacted to form 2,3-dimethoxy, which is represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents the above meaning] A method for synthesizing 2,3-dimethoxy-5-substituted-6-methyl-benzohydroquinone, characterized in that a silica-alumina compound is used as a reaction catalyst when synthesizing -5-substituted-6-methyl-benzohydroquinone. 2 2,3-dimethoxy-5-methyl-benzohydroquinone represented by the following chemical formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or its isoform ▲ Mathematical formula , chemical formulas, tables, etc. ▼ [In the formula, R represents the group of the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where n is an integer from 0 to 9, A and B are hydrogen atoms or A- B represents the formation of a bond. ] (iso)prenol or its reactive derivative is reacted to form 2,3-dimethoxy, which is represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents the above meaning] When synthesizing -5-substituted-6-methyl-benzohydroquinone, a silica-alumina compound was used as a reaction catalyst, and the obtained 2,3-
The following formula ▲ formula, characterized by treating dimethoxy-5-substituted-6-methyl-benzohydroquinone with an oxidizing agent,
Synthesis of 2,3-dimethoxy-5-substituted-6-methyl-1,4-benzoquinone represented by chemical formulas, tables, etc.▼ [In the formula, R represents the above meaning].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50113727A JPS601292B2 (en) | 1975-09-22 | 1975-09-22 | Synthesis method of dihydrocoenzyme Q compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50113727A JPS601292B2 (en) | 1975-09-22 | 1975-09-22 | Synthesis method of dihydrocoenzyme Q compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5239636A JPS5239636A (en) | 1977-03-28 |
| JPS601292B2 true JPS601292B2 (en) | 1985-01-14 |
Family
ID=14619599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50113727A Expired JPS601292B2 (en) | 1975-09-22 | 1975-09-22 | Synthesis method of dihydrocoenzyme Q compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS601292B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61231976A (en) * | 1985-04-05 | 1986-10-16 | Bibun Corp | Production of marine fish paste product and apparatus therefor |
| JPH0148746B2 (en) * | 1985-01-18 | 1989-10-20 | Bibun Corp |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5959763A (en) * | 1982-09-30 | 1984-04-05 | Ube Ind Ltd | Modified polyethylene adhesive |
| JPS6014791A (en) * | 1983-07-04 | 1985-01-25 | 松下電器産業株式会社 | Heater |
| JPS6028195A (en) * | 1983-07-27 | 1985-02-13 | 松下電器産業株式会社 | Heater |
| US20090246185A1 (en) * | 2006-03-13 | 2009-10-01 | Kaneka Corporation | Cardiac dysfunction-ameliorating agent or cardiac function-maintaining agent |
-
1975
- 1975-09-22 JP JP50113727A patent/JPS601292B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0148746B2 (en) * | 1985-01-18 | 1989-10-20 | Bibun Corp | |
| JPS61231976A (en) * | 1985-04-05 | 1986-10-16 | Bibun Corp | Production of marine fish paste product and apparatus therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5239636A (en) | 1977-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0022162A1 (en) | Process for producing disubstituted 4-hydroxycyclopentenones; monosubstituted cyclopentendiones and 4-hydroxycyclopentenones | |
| US4127608A (en) | Synthesis of Vitamin E | |
| JPS601292B2 (en) | Synthesis method of dihydrocoenzyme Q compounds | |
| US4482493A (en) | Method for preparing benzoquinones | |
| EP0012824B1 (en) | Process for the manufacture of alpha-tocopherol and novel intermediate in this process | |
| JPS6020368B2 (en) | Production method of 1,4 benzohydroquinone derivative | |
| US4310465A (en) | Synthesis of vitamin E and quinone intermediates | |
| US4061660A (en) | Process for synthesis of coenzyme Q compounds | |
| US4089873A (en) | Preparation of menaquinones | |
| Castedo et al. | Selective reductive carbonyl couplings with titanium | |
| US4163864A (en) | Process for preparing 2-methyl-3-prenyl-4,5,6-trimethoxyphenol | |
| Nakazaki et al. | Syntheses and chemical characterization of tris-bridged [2.2. 2] cyclophanes with a triphenylmethyl component | |
| EP0169688A1 (en) | Process for preparing anti-inflammatory cycloalkylidenemethylphenylacetic acid derivatives | |
| JPS5925772B2 (en) | Synthesis method of supplementary element Q class compounds | |
| US4243598A (en) | Synthesis of vitamin E | |
| JPS6035347B2 (en) | Synthesis method of α-tocopherol | |
| US3036106A (en) | Alkyl and acyl ferrocenes | |
| US4252726A (en) | Preparation of dl-α-tocopherol | |
| EP0537954B1 (en) | Process of preparing diphenylmethane derivatives | |
| EP0331422A2 (en) | Method of preparing 2-acylresorcinols | |
| JPS5929173B2 (en) | Method for producing dihydrocoenzyme Q compound | |
| US4159993A (en) | 3-Metallo substituted naphthalenes | |
| JPS5826327B2 (en) | Hokosokyuuruino Goseihou | |
| Von Werner et al. | The synthesis and some reactions of pentafluoroethyl vinyl ketone | |
| SU440820A1 (en) |