JPH0454656B2 - - Google Patents
Info
- Publication number
- JPH0454656B2 JPH0454656B2 JP58190573A JP19057383A JPH0454656B2 JP H0454656 B2 JPH0454656 B2 JP H0454656B2 JP 58190573 A JP58190573 A JP 58190573A JP 19057383 A JP19057383 A JP 19057383A JP H0454656 B2 JPH0454656 B2 JP H0454656B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- reaction
- parts
- benzoquinone
- general formula
- 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
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical class CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims description 4
- MSVRGYOYISBGTH-UHFFFAOYSA-N 4-methoxy-2-methylbenzoic acid Chemical class COC1=CC=C(C(O)=O)C(C)=C1 MSVRGYOYISBGTH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical class O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 238000000605 extraction Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- IINQNMKCOMHAMZ-UHFFFAOYSA-N 2,3,4-trimethoxy-6-methylbenzoic acid Chemical compound COC1=CC(C)=C(C(O)=O)C(OC)=C1OC IINQNMKCOMHAMZ-UHFFFAOYSA-N 0.000 description 2
- VJVOAGLABGZRSL-UHFFFAOYSA-N 2-methoxy-5-methylcyclohexa-2,5-diene-1,4-dione Chemical compound COC1=CC(=O)C(C)=CC1=O VJVOAGLABGZRSL-UHFFFAOYSA-N 0.000 description 2
- KCIZTNZGSBSSRM-UHFFFAOYSA-N 3,4,5-Trimethoxytoluene Chemical compound COC1=CC(C)=CC(OC)=C1OC KCIZTNZGSBSSRM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- ACTIUHUUMQJHFO-UPTCCGCDSA-N coenzyme Q10 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UPTCCGCDSA-N 0.000 description 2
- 235000017471 coenzyme Q10 Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- -1 etc. Chemical compound 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000004057 1,4-benzoquinones Chemical class 0.000 description 1
- SHLREVJOFPNLPQ-UHFFFAOYSA-N 2,3-dimethoxy-6-methylbenzoic acid Chemical compound COC1=CC=C(C)C(C(O)=O)=C1OC SHLREVJOFPNLPQ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ACTIUHUUMQJHFO-UHFFFAOYSA-N Coenzym Q10 Natural products COC1=C(OC)C(=O)C(CC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- NPCOQXAVBJJZBQ-UHFFFAOYSA-N reduced coenzyme Q9 Natural products COC1=C(O)C(C)=C(CC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)CCC=C(C)C)C(O)=C1OC NPCOQXAVBJJZBQ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229940035936 ubiquinone Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、一般式（）
（式中、R1は低級アルコキシ基を示し、R2は水
素原子または低級アルコキシ基を示す。）
で示される２−メチル−１，４−ベンゾキノン誘
導体の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula () (In the formula, R 1 represents a lower alkoxy group, and R 2 represents a hydrogen atom or a lower alkoxy group.)
上記一般式（）で示される２−メチル−１，
４−ベンゾキノン誘導体は医薬、農薬等の重要な
中間体であり、特にR1およびR2がメトキシ基を
形成している２，３−ジメトキシ−５−メチル−
１，４−ベンゾキシノンはコエンザイムＱとかユ
ビキノンなどと呼ばれる一連の物質の原料となる
ものである。 2-methyl-1 represented by the above general formula (),
4-Benzoquinone derivatives are important intermediates for medicines, agricultural chemicals, etc., and in particular 2,3-dimethoxy-5-methyl-, where R 1 and R 2 form a methoxy group.
1,4-Benzoxinone is a raw material for a series of substances called coenzyme Q and ubiquinone.
従来、一般式（）で示される２−メチル−
１，４−ベンゾキノン誘導体の製造法としては
種々検討されているが、工業的に満足し得る方法
は未だ確立されていない。特に、２，３−ジメト
キシ−５−メチル−１，４−ベンゾキノンの製造
法については種々検討されているが、その方法は
いずれも出発原料の入手が困難である、反応工程
が長い、目的物の収率が低い等の欠点を有してい
る。 Conventionally, 2-methyl- represented by the general formula ()
Although various methods for producing 1,4-benzoquinone derivatives have been studied, no industrially satisfactory method has been established yet. In particular, various methods for producing 2,3-dimethoxy-5-methyl-1,4-benzoquinone have been studied, but all of these methods involve difficulty in obtaining starting materials, long reaction steps, or the production of the desired product. It has disadvantages such as low yield.
これらのうち、比較的優れた方法として、３，
４，５−トリアルコキシトルエンを酸化する方法
が知られているが（特公昭47−18740号公報）、こ
の方法は酸化速度が極めて遅く、反応時間として
２〜５日間もの長時間を要し、また、副生物が多
いことから繁雑な後処理を必要とするなど工業的
に有利な方法とは言い難い。 Among these methods, 3.
A method of oxidizing 4,5-trialkoxytoluene is known (Japanese Patent Publication No. 47-18740), but this method has an extremely slow oxidation rate and requires a long reaction time of 2 to 5 days. Furthermore, it is difficult to say that it is an industrially advantageous method as it requires complicated post-processing due to the large amount of by-products.
このような状況下で、本発明者らは前記一般式
（）で示される２−メチル−１，４−ベンゾキ
ノン誘導体の新しい製造法について研究した結
果、従来の各種合成法のもつ欠点を解決し、短時
間で、好収率で目的物を得る方法を見出し、本発
明に至つた。 Under these circumstances, the present inventors conducted research on a new method for producing the 2-methyl-1,4-benzoquinone derivative represented by the above general formula (), and as a result, they solved the drawbacks of various conventional synthesis methods. discovered a method for obtaining the desired product in a short time and in good yield, leading to the present invention.
すなわち本発明は、一般式（）
（式中、R1およびR2は前記と同じ意味を有す
る。）
で示される４−メトキシ−６−メチル安息香酸誘
導体と重クロム酸塩と反応させることを特徴とす
る前記一般式（）で示される２−メチル−１，
４−ベンゾキノン誘導体の製造法を提供するもの
である。 That is, the present invention provides general formula () (In the formula, R 1 and R 2 have the same meanings as above.) In the general formula (), the 4-methoxy-6-methylbenzoic acid derivative represented by the formula (2) is reacted with a dichromate. 2-methyl-1 as indicated,
A method for producing a 4-benzoquinone derivative is provided.
本発明において原料として用いられる４−メト
キシ−６−メチル安息香酸誘導体、たとえば２，
３，４−トリメトキシ−６−メチル安息香酸は
３，４，５−トリメトキシトルエンをブロム化
後、マグネシウムと反応させてグリニヤール試薬
とし、これを炭酸ガスと反応させた後、加水分解
する方法、あるいは、３，４，５−トリメトキシ
トルエンのガツターマンのアルデヒド合成法、リ
ーマーチイマン反応またはビルスマイヤー反応な
どにより得られるアルデヒドを酸化することによ
り容易に製造することができる。 4-methoxy-6-methylbenzoic acid derivatives used as raw materials in the present invention, such as 2,
3,4-trimethoxy-6-methylbenzoic acid is obtained by brominating 3,4,5-trimethoxytoluene, reacting it with magnesium to obtain a Grignard reagent, reacting it with carbon dioxide gas, and then hydrolyzing it. Alternatively, it can be easily produced by oxidizing an aldehyde obtained by Gutterman's aldehyde synthesis method of 3,4,5-trimethoxytoluene, Riemer-Tschijmann reaction, Vilsmeier reaction, or the like.
本発明で使用する酸化剤としては従来より公知
のものが広く使用でき、たとえば重クロム酸ソー
ダ、過マンガン酸カリ、過酢酸、過硫酸アンモ
ン、塩化第二鉄、硫酸第２鉄、無水クロム酸、二
酸化マンガンなどが例示されるが、好ましくは重
クロム酸ソーダである。 As the oxidizing agent used in the present invention, a wide variety of conventionally known oxidizing agents can be used, such as sodium dichromate, potassium permanganate, peracetic acid, ammonium persulfate, ferric chloride, ferric sulfate, and chromic anhydride. , manganese dioxide, etc., and sodium dichromate is preferred.
酸化剤の使用量は特に制限されないが、一般に
は４−メトキシ−６−メチル安息香酸誘導体に対
して0.1〜30重量倍である。 The amount of the oxidizing agent used is not particularly limited, but is generally 0.1 to 30 times the amount by weight of the 4-methoxy-6-methylbenzoic acid derivative.
反応溶媒としては、例えば水、ベンゼン、トル
エン、メタノール、アセトン、ジメチルホルムア
ミド、ジメチルスルホキシド、エチレンジクロラ
イド、クロロホルム等の反応に不活性な溶媒の単
独、又は混合物が使用される。 As the reaction solvent, for example, water, benzene, toluene, methanol, acetone, dimethylformamide, dimethyl sulfoxide, ethylene dichloride, chloroform, and other solvents inert to the reaction may be used alone or in mixtures.
反応温度は通常０〜150℃の範囲で任意である
が、好ましくは10〜100℃の範囲である。 The reaction temperature is generally arbitrary in the range of 0 to 150°C, but preferably in the range of 10 to 100°C.
反応後、目的物質は通常の方法、例えば抽出、
蒸留等の方法で反応液から容易に分離することが
出来る。 After the reaction, the target substance is extracted using conventional methods such as extraction,
It can be easily separated from the reaction solution by methods such as distillation.
抽出処理を行う場合、抽出溶媒としてはトルエ
ン、メチルイソブチルケトン、エーテル、エチレ
ンジクロライド等が用いられ、抽出有機層を無水
硫酸ナトリウムなどで乾燥後、溶媒を留去するこ
とにより目的物が得られる。 When performing the extraction process, toluene, methyl isobutyl ketone, ether, ethylene dichloride, etc. are used as the extraction solvent, and the target product is obtained by drying the extracted organic layer over anhydrous sodium sulfate or the like, and then distilling off the solvent.
反応後から単離された２−メチル−１，４−ベ
ンゾキノン誘導体は必要により公知の方法たとえ
ば再結晶などの方法で更に精製することができ
る。 The 2-methyl-1,4-benzoquinone derivative isolated after the reaction can be further purified, if necessary, by a known method such as recrystallization.
かくして、本発明の方法によれば、短時間で、
好収率で目的とする２−メチル−１，４−ベンゾ
キノン誘導体を製造することができる。 Thus, according to the method of the present invention, in a short time,
The desired 2-methyl-1,4-benzoquinone derivative can be produced in good yield.
以下、実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
撹拌装置、温度計、水冷却管を装着した４ツ口
フラスコに２，３，４−トリメトキシ−６−メチ
ル安息香酸１重量部を仕込み、15％硫酸100容量
部およびトルエン200容量部を加えて溶解させた
のち重クロム酸ソーダ２重量部を加え、室温下で
３時間反応させる。（反応終点はTLGで原料がな
くなつた点をもつて終点とする。）
反応終了後、反応液から油層を分液し、水洗
し、無水芒硝で乾燥後、溶媒を留去することによ
り、２，３−ジメトキシ−５−メチル−１，４−
ベンゾキノン0.74重量部を得た。Example 1 1 part by weight of 2,3,4-trimethoxy-6-methylbenzoic acid was charged into a four-neck flask equipped with a stirrer, a thermometer, and a water condenser, and 100 parts by volume of 15% sulfuric acid and 200 parts by volume of toluene were added. After adding and dissolving 2 parts by weight of sodium dichromate, the mixture was allowed to react at room temperature for 3 hours. (The end point of the reaction is defined as the point at which the raw material is exhausted in TLG.) After the reaction is completed, the oil layer is separated from the reaction solution, washed with water, dried with anhydrous sodium sulfate, and then the solvent is distilled off. 2,3-dimethoxy-5-methyl-1,4-
0.74 parts by weight of benzoquinone was obtained.
（収率92％）
融点 59〜60℃（橙赤色針状結晶）
元素分析値 C9H10O4
Ｃ(%) Ｈ(%)
計算値 59.88 5.53
実測値 59.41 5.51
参考例 １
実施例１で用いたと同様のフラスコに２，３，
４−トリメトキシ−６−メチル安息香酸１重量部
を仕込み、メタノール５容量部33％硫酸３容量部
を加えて溶解させ、これに過硫酸アンモン2.5重
量部を水40容量部に溶解させた溶液を滴下する。(Yield 92%) Melting point 59-60°C (orange red needle crystals) Elemental analysis value C 9 H 10 O 4 C(%) H(%) Calculated value 59.88 5.53 Actual value 59.41 5.51 Reference example 1 In Example 1 In the same flask as used, add 2, 3,
Charge 1 part by weight of 4-trimethoxy-6-methylbenzoic acid, add 5 parts by volume of methanol and 3 parts by volume of 33% sulfuric acid to dissolve it, and add a solution of 2.5 parts by weight of ammonium persulfate dissolved in 40 parts by volume of water. Drip.
滴下後、50℃で８時間反応させる。反応終了
後、反応後に水200容量部を加え、トルエンで抽
出する。トルエン層を５％炭酸水素ナトリウム水
溶液及び水で洗浄した後、無水硫酸ナトリウムで
乾燥後、容媒を留去することによつて、２，３−
ジメトキシ−５−メチル−１，４−ベンゾキノン
0.43重量部を得る。（収率53.6％）
実施例 ２
実施例１で用いたと同様のフラスコに３，４−
ジメトキシ−６−メチル安息香酸１重量部を仕込
み、15％硫酸100容量部およびトルエン200容量部
を加えて溶解させたのち重クロム酸ソーダ4.5重
量部を加え、50〜55℃で７時間反応させる。 After dropping, react at 50°C for 8 hours. After the reaction is complete, add 200 parts by volume of water and extract with toluene. 2,3-
Dimethoxy-5-methyl-1,4-benzoquinone
Obtain 0.43 parts by weight. (Yield 53.6%) Example 2 Into the same flask as used in Example 1, 3,4-
Charge 1 part by weight of dimethoxy-6-methylbenzoic acid, add 100 parts by volume of 15% sulfuric acid and 200 parts by volume toluene to dissolve, add 4.5 parts by weight of sodium dichromate, and react at 50 to 55°C for 7 hours. .
反応終了後、実施例１と同様に処理して２−メ
トキシ−５−メチル−１，４−ベンゾキノン0.68
重量部を得る。 After the reaction was completed, the same procedure as in Example 1 was carried out to obtain 0.68% of 2-methoxy-5-methyl-1,4-benzoquinone.
Obtain parts by weight.
（収率 88％） 融点172〜173℃（黄色針状結晶） 元素分析値 C8H8O3 Ｃ(%) Ｈ(%) 計算値 63.15 5.30 実測値 62.83 5.38(Yield 88%) Melting point 172-173℃ (yellow needle crystals) Elemental analysis value C 8 H 8 O 3 C (%) H (%) Calculated value 63.15 5.30 Actual value 62.83 5.38
Claims (1)
素原子または低級アルコキシ基を示す。） で示される４−メトキシ−６−メチル安息香酸誘
導体と重クロム酸塩とを反応させることを特徴と
する一般式 （式中、R1およびR2は前記と同じ意味を有す
る。） で示される２−メチル−１，４−ベンゾキノン誘
導体の製造法。[Claims] 1. General formula (In the formula, R 1 represents a lower alkoxy group, and R 2 represents a hydrogen atom or a lower alkoxy group.) Reacting a 4-methoxy-6-methylbenzoic acid derivative represented by the following with a dichromate. Featured general formula (In the formula, R 1 and R 2 have the same meanings as above.) A method for producing a 2-methyl-1,4-benzoquinone derivative represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19057383A JPS6081141A (en) | 1983-10-11 | 1983-10-11 | Production of 2-methyl-1,4-benzoquinone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19057383A JPS6081141A (en) | 1983-10-11 | 1983-10-11 | Production of 2-methyl-1,4-benzoquinone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6081141A JPS6081141A (en) | 1985-05-09 |
| JPH0454656B2 true JPH0454656B2 (en) | 1992-08-31 |
Family
ID=16260307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19057383A Granted JPS6081141A (en) | 1983-10-11 | 1983-10-11 | Production of 2-methyl-1,4-benzoquinone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6081141A (en) |
-
1983
- 1983-10-11 JP JP19057383A patent/JPS6081141A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6081141A (en) | 1985-05-09 |
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