JPH0567617B2 - - Google Patents
Info
- Publication number
- JPH0567617B2 JPH0567617B2 JP63291666A JP29166688A JPH0567617B2 JP H0567617 B2 JPH0567617 B2 JP H0567617B2 JP 63291666 A JP63291666 A JP 63291666A JP 29166688 A JP29166688 A JP 29166688A JP H0567617 B2 JPH0567617 B2 JP H0567617B2
- Authority
- JP
- Japan
- Prior art keywords
- dimethoxybenzonitrile
- hydroxy
- compound
- hydrogen peroxide
- solvent
- 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
- -1 dimethoxybenzonitrile compound Chemical class 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 29
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 12
- 235000019253 formic acid Nutrition 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RYRZSQQELLQCMZ-UHFFFAOYSA-N 2,4-dimethoxybenzonitrile Chemical compound COC1=CC=C(C#N)C(OC)=C1 RYRZSQQELLQCMZ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XHAHKSSLDJIEDH-UHFFFAOYSA-N 2,6-dimethoxybenzonitrile Chemical compound COC1=CC=CC(OC)=C1C#N XHAHKSSLDJIEDH-UHFFFAOYSA-N 0.000 description 2
- JKPLQGXXESDJLY-UHFFFAOYSA-N 4-hydroxy-3,5-dimethoxybenzonitrile Chemical compound COC1=CC(C#N)=CC(OC)=C1O JKPLQGXXESDJLY-UHFFFAOYSA-N 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical class OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 1
- NVTHWSJNXVDIKR-UHFFFAOYSA-N 3,5-dimethoxybenzonitrile Chemical compound COC1=CC(OC)=CC(C#N)=C1 NVTHWSJNXVDIKR-UHFFFAOYSA-N 0.000 description 1
- YMWYSWXWDNMUIX-UHFFFAOYSA-N 4-hydroxy-2,3-dimethoxybenzaldehyde Chemical compound COC1=C(O)C=CC(C=O)=C1OC YMWYSWXWDNMUIX-UHFFFAOYSA-N 0.000 description 1
- YIEQOGHMZPTDLB-UHFFFAOYSA-N 4-hydroxy-2,3-dimethoxybenzonitrile Chemical class COC1=C(O)C=CC(C#N)=C1OC YIEQOGHMZPTDLB-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000006203 ethylation Effects 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
〔産業上の利用分野〕
本発明は、ヒドロキシ−ジメトキシベンゾニト
リル化合物の製造方法に関するものである。
さらに詳しくは、ギ酸を溶媒かつ触媒として過
酸化水素を酸化剤として用いてジメトキシベンゾ
ニトリル化合物を酸化して効率よくヒドロキシ−
ジメトキシベンゾニトリル化合物を製造する方法
に関するものである。
〔従来技術及びその問題点〕
ヒドロキシ−ジメトキシベンゾニトリル化合物
は、水酸基及びシアノ基という反応性に富んだ官
能基を２つ有する化合物であり、様々な誘導体が
容易に合成可能である。たとえば、シアノ基を加
水分解によりカルボキシル基に、還元によりアミ
ノメチル基に誘導可能であり、水酸基はメチル
化、エチル化などにより、メトキシ基、エトキシ
基などに容易に誘導できる。又、４−ヒドロキシ
−３，５−ジメトキシベンゾニトリルは写真のか
ぶり防止剤として有効であると報告されている
（U.S.Patent4252893）。ところが、これらのヒド
ロキシベンゾニトリル化合物を製造するための従
来の諸方法は原料の入手が困難であり（ヒドロキ
シ−ジメトキシベンズアルデヒドとヒドロキシル
アミンとの反応、Chem.Pharm.Bull.、32、
（1984）、4466）、毒性の強いシアノ第一銅を使用
したり（Chem.Pharm.Bull.、32，（1984）、
2296）、重金属イオンなどの産業廃棄物を副生す
るものであつた。
〔発明の課題〕
本発明は、入手容易な原料からヒドロキシ−ジ
メトキシベンゾニトリル化合物を工業的に有利に
製造する方法を提供することをその課題とする。
〔課題を解決するための手段〕
そこで、本発明は、ジメトキシベンゾニトリル
化合物を過酸化水素で酸化し、ヒドロキシ−ジメ
トキシベンゾニトリル化合物を製造する際の溶媒
及び酸化触媒について鋭意研究を重ねた結果、ギ
酸を溶媒及び酸化触媒として使用することによ
り、比較的高収率で目的とするヒドロキシ−ジメ
トキシベンゾニトリル化合物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つ
た。
すなわち、本発明は、ジメトキシベンゾニトリ
ル化合物を過酸化水素と反応させて、ヒドロキシ
−ジメトキシベンゾニトリル化合物を製造するに
あたり、ギ酸を溶媒及び酸化触媒として使用する
ことを特徴とするヒドロキシ−ジメトキシベンゾ
ニトリル化合物の製造方法を提供するものであ
る。
本発明における反応方法は、ジメトキシベンゾ
ニトリル化合物と過酸化水素をギ酸溶媒中、温和
な条件下で単に混合撹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。
本発明においては、ジメトキシベンゾニトリル
化合物を酸化するために、酸化剤として過酸化水
素を用いるとともに、ギ酸を溶媒及び酸化触媒と
して使用する。過酸化水素源としては、過酸化水
素水が好ましく用いられる。過酸化水素水として
は、各種濃度のものが入手できるが、一般に市販
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。原料がギ酸に溶けにくい
場合は、酢酸などの水溶性の有機溶媒を添加する
事も可能である。
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、
０〜100℃、好ましくは10〜70℃に保つのがよい。
反応時間は、過酸化水素水の濃度ならびに使用量
に左右されるが、通常は１〜24時間で十分であ
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ヒドロキシ−ジ
メトキシベンゾニトリル化合物を含む固体が得ら
れる。このものをカラムクロマトグラフイー、分
別結晶などにより分離し、NMR、IR、及びマス
スペクトルから同定し、さらに水素基をメチル化
した化合物と別途に合成した標品との上記のスペ
クトルの一致により確認した。
〔発明の効果〕
本発明方法に従うと、ジメトキシベンゾニトリ
ル化合物からヒドロキシ−ジメトキシベンゾニト
リル化合物を一段階で、しかも比較的高い収率で
得ることができる上に、使用する酸化剤が過酸化
水素で、酸化剤からの副生物は水のみであること
から、従来法の欠陥であつた産業廃棄物を副生す
ること等の欠点が除かれるので、工業的なヒドロ
キシ−ジメトキシベンゾニトリル化合物の製造方
法として好適である。
しかも、本発明で用いるジメトキシベンゾニト
リル化合物は、ジヒドロキシベンゾニトリル化合
物のメチル化により容易にかつ高収率で合成する
ことができるので、本発明は原料コストの面から
も非常に有利な方法である。
さらに、本発明によれば、下記式（）〜
（）で表わされる新規なヒドロキシ−ジメトキ
シベンゾニトリル化合物をも合成することができ
る。
[Industrial Field of Application] The present invention relates to a method for producing a hydroxy-dimethoxybenzonitrile compound. More specifically, dimethoxybenzonitrile compound is efficiently oxidized using formic acid as a solvent and catalyst and hydrogen peroxide as an oxidizing agent.
The present invention relates to a method for producing a dimethoxybenzonitrile compound. [Prior Art and its Problems] A hydroxy-dimethoxybenzonitrile compound is a compound having two highly reactive functional groups, a hydroxyl group and a cyano group, and various derivatives can be easily synthesized. For example, a cyano group can be induced into a carboxyl group by hydrolysis and an aminomethyl group by reduction, and a hydroxyl group can be easily induced into a methoxy group, an ethoxy group, etc. by methylation, ethylation, etc. It has also been reported that 4-hydroxy-3,5-dimethoxybenzonitrile is effective as a photographic antifoggant (US Patent 4252893). However, conventional methods for producing these hydroxybenzonitrile compounds have difficulty in obtaining raw materials (reaction of hydroxy-dimethoxybenzaldehyde with hydroxylamine, Chem.Pharm.Bull., 32;
(1984), 4466), the use of highly toxic cuprous cyano (Chem.Pharm.Bull., 32, (1984),
2296), which was a by-product of industrial waste such as heavy metal ions. [Problem of the Invention] An object of the present invention is to provide an industrially advantageous method for producing a hydroxy-dimethoxybenzonitrile compound from readily available raw materials. [Means for Solving the Problems] Accordingly, the present invention has been made as a result of extensive research on the solvent and oxidation catalyst when producing a hydroxy-dimethoxybenzonitrile compound by oxidizing a dimethoxybenzonitrile compound with hydrogen peroxide. The inventors have discovered that the desired hydroxy-dimethoxybenzonitrile compound can be produced in relatively high yield by using formic acid as a solvent and an oxidation catalyst, and based on this finding, the present invention has been accomplished. That is, the present invention provides a hydroxy-dimethoxybenzonitrile compound characterized in that formic acid is used as a solvent and an oxidation catalyst in producing the hydroxy-dimethoxybenzonitrile compound by reacting the dimethoxybenzonitrile compound with hydrogen peroxide. The present invention provides a method for manufacturing. The reaction method of the present invention can be easily achieved by simply mixing and stirring a dimethoxybenzonitrile compound and hydrogen peroxide in a formic acid solvent under mild conditions, and is an extremely simple and safe oxidation method. In the present invention, in order to oxidize the dimethoxybenzonitrile compound, hydrogen peroxide is used as an oxidizing agent, and formic acid is used as a solvent and an oxidation catalyst. As the hydrogen peroxide source, hydrogen peroxide solution is preferably used. Hydrogen peroxide solutions are available in various concentrations, ranging from the commercially available 30% to higher concentrations of 50 to 60%. If the raw material is difficult to dissolve in formic acid, it is also possible to add a water-soluble organic solvent such as acetic acid. The reaction temperature in this reaction does not require particularly strict control, but the reaction is preferably around room temperature.
The temperature is preferably maintained at 0 to 100°C, preferably 10 to 70°C.
The reaction time depends on the concentration of the hydrogen peroxide solution and the amount used, but 1 to 24 hours is usually sufficient. After the reaction is complete, water is added and extracted with a water-insoluble organic solvent such as methylene chloride. After drying over magnesium sulfate, the solvent is distilled off to obtain a solid containing the hydroxy-dimethoxybenzonitrile compound. This substance was separated by column chromatography, fractional crystallization, etc., identified from NMR, IR, and mass spectra, and further confirmed by the match of the above spectrum between the compound with methylated hydrogen groups and a separately synthesized standard. did. [Effects of the Invention] According to the method of the present invention, a hydroxy-dimethoxybenzonitrile compound can be obtained from a dimethoxybenzonitrile compound in one step and in a relatively high yield, and the oxidizing agent used is hydrogen peroxide. Since the by-product from the oxidizing agent is only water, the drawbacks of the conventional method, such as the production of industrial waste as a by-product, are eliminated, so this is an industrial method for producing hydroxy-dimethoxybenzonitrile compounds. It is suitable as Moreover, the dimethoxybenzonitrile compound used in the present invention can be easily synthesized in high yield by methylation of a dihydroxybenzonitrile compound, so the present invention is a very advantageous method in terms of raw material cost. . Furthermore, according to the present invention, the following formula () ~
A novel hydroxy-dimethoxybenzonitrile compound represented by () can also be synthesized.
【式】【formula】
次に本発明を実施例によりさらに詳細に説明す
る。
実施例 １
ガラス製フラスコに２，４−ジメトキシベンゾ
ニトリル４ｍmolをギ酸10mlに溶かし、31％過酸
化水素水を２ml滴下した。窒素雰囲気下、温度を
40℃に保ちながら２時間撹拌を続けた。反応終了
後、水を50ml加え、20mlの塩化メチレンで３回抽
出した。抽出液を、硫酸マグネシウムで乾燥後、
ガスクロマトグラフにより分析した結果、反応率
59％のところで、３−ヒドロキシ−２，４−ジメ
トキシベンゾニトリルが収率10％、選択率17％、
５−ヒドロキシ−２，４−ジメトキシベンゾニト
リルが収率18％、選択率31％で得られた。
（３−ヒドロキシ−２，４−ジメトキシベンゾ
ニトリル）NMR（CDCl3）：δ3.94（3H、Ｓ）、4.08
（3H、Ｓ），5.69（1H、Ｓ）、6.65、7.14（2H、
ABq、Ｊ＝９Hz）；IR（KBr）：3304、2226、
1605、1499、1296、1218、1098、808（cm-1）；質
量分析：ｍ／e.（相対強度）179（M+、100）、164
（26）、136（44）、93（20）。
（５−ヒドロキシ−２、４−ジメトキシベンゾ
ニトリル）NMR（CDCl3）：δ3.90（3H、Ｓ）、3.97
（3H、Ｓ）、5.38（1H、Ｓ）、6.51（1H、Ｓ）、7.07
（1H；IR（KBr）、Ｓ）：3334、2226、1520、
1294、1276、1214、1029、859（cm-1）；質量分
析：ｍ／ｅ；（相対強度）179（M+、96）、164
（100）、136（28）、53（20）。
実施例 ２
実施例１と同様な方法により、３，５−ジメト
キシベンゾニトリルをギ酸溶媒中31％過酸化水素
水１mlで40℃、２時間酸化したところ、反応率35
％のところで、４−ヒドロキシ−３，５−ジメト
キシベンゾニトリルが収率４％、選択率11％、２
−ヒドロキシ−３，５−ジメトキシベンゾニトリ
リが収率10％、選択率29％で得られた。
（２−ヒドロキシ−３，５−ジメトキシベンゾ
ニトリル）NMR（CDCl3）：δ3.88（3H、Ｓ）、3.91
（3H、Ｓ）、5.38（1H、br）、6.52（1H、ｄ、Ｊ＝
３Hz）；6.66（1H、ｄ、Ｊ＝３Hz）；質量分析：
ｍ／ｅ、（相対強度）179（M+、100）、164（73）、
136（32）、53（21）。
実施例 ３
実施例１と同様な方法により、２，６−ジメト
キシベンゾニトリルをギ酸溶媒中31％過酸化水素
２mlで40℃で、２時間酸化したところ、３−ヒド
ロキシ−２，６−ジメトキシベンゾニトリルが反
応率61％、収率39％、選択率64％で得られた。
（３−ヒドロキシ−２，６−ジメトキシベンゾ
ニトリル）NMR（CDCl39：δ3.85（3H、Ｓ）、4.11
（3H、Ｓ）、5.50（1H、Ｓ）、6.67、7.10（2H、
HBq、Ｊ＝９Hz）：1R（KBr）：3326、2246、
1510、1267、1100；質量分析：ｍ／ｅ、（相対強
度）179（M-、100）、164（70）、136（62）、108
（17）。
実施例 ４
実施例１と同様な方法により、２，４−ジメト
キシベンゾニトリルをギ酸溶媒中６％過酸化水素
水１mlで40℃、２時間酸化したところ、反応率55
％のところで、３−ヒドロキシ−２，４−ジメト
キシベンゾニトリルが収率％、選択率18％、５−
ヒドロキシ−２，４−ジメトキシベンゾニトリル
が収率19％、選択率35％で得られた。
実施例 ５
実施例１と同様な方法により、２，６−ジメト
キシベンゾニトリルをギ酸溶媒中60％過酸化水素
水１mlで40℃、２時間酸化したところ、３−ヒド
ロキシ−２，６−ジメトキシベンゾニトリルが反
応率74％、収率40％、選択率54％で得られた。
比較例 １
実施例１において、溶媒として酢酸を用いたと
ころ、２，４−ジメトキシベンゾニトリルが100
％そのまま回収された。
Next, the present invention will be explained in more detail with reference to Examples. Example 1 4 mmol of 2,4-dimethoxybenzonitrile was dissolved in 10 ml of formic acid in a glass flask, and 2 ml of 31% hydrogen peroxide solution was added dropwise. Under nitrogen atmosphere, temperature
Stirring was continued for 2 hours while maintaining the temperature at 40°C. After the reaction was completed, 50 ml of water was added, and the mixture was extracted three times with 20 ml of methylene chloride. After drying the extract with magnesium sulfate,
As a result of gas chromatograph analysis, the reaction rate was
At 59%, the yield of 3-hydroxy-2,4-dimethoxybenzonitrile was 10%, the selectivity was 17%,
5-hydroxy-2,4-dimethoxybenzonitrile was obtained in a yield of 18% and a selectivity of 31%. (3-hydroxy-2,4-dimethoxybenzonitrile) NMR ( CDCl3 ): δ3.94 (3H,S), 4.08
(3H, S), 5.69 (1H, S), 6.65, 7.14 (2H,
ABq, J=9Hz); IR (KBr): 3304, 2226,
1605, 1499, 1296, 1218, 1098, 808 (cm -1 ); Mass spectrometry: m/e. (relative intensity) 179 (M + , 100), 164
(26), 136(44), 93(20). (5-hydroxy-2,4-dimethoxybenzonitrile) NMR ( CDCl3 ): δ3.90 (3H,S), 3.97
(3H, S), 5.38 (1H, S), 6.51 (1H, S), 7.07
(1H; IR (KBr), S): 3334, 2226, 1520,
1294, 1276, 1214, 1029, 859 (cm -1 ); Mass spectrometry: m/e; (relative intensity) 179 (M + , 96), 164
(100), 136(28), 53(20). Example 2 In the same manner as in Example 1, 3,5-dimethoxybenzonitrile was oxidized with 1 ml of 31% hydrogen peroxide in a formic acid solvent at 40°C for 2 hours, and the reaction rate was 35.
%, the yield of 4-hydroxy-3,5-dimethoxybenzonitrile was 4%, the selectivity was 11%, and 2
-Hydroxy-3,5-dimethoxybenzonitrile was obtained with a yield of 10% and a selectivity of 29%. (2-Hydroxy-3,5-dimethoxybenzonitrile) NMR ( CDCl3 ): δ3.88 (3H,S), 3.91
(3H, S), 5.38 (1H, br), 6.52 (1H, d, J=
3Hz); 6.66 (1H, d, J=3Hz); Mass spectrometry:
m/e, (relative intensity) 179 (M + , 100), 164 (73),
136(32), 53(21). Example 3 In the same manner as in Example 1, 2,6-dimethoxybenzonitrile was oxidized with 2 ml of 31% hydrogen peroxide in a formic acid solvent at 40°C for 2 hours, resulting in 3-hydroxy-2,6-dimethoxybenzonitrile. Nitrile was obtained with a reaction rate of 61%, a yield of 39%, and a selectivity of 64%. (3-Hydroxy-2,6-dimethoxybenzonitrile) NMR (CDCl 3 9: δ3.85 (3H,S), 4.11
(3H, S), 5.50 (1H, S), 6.67, 7.10 (2H,
HBq, J=9Hz): 1R (KBr): 3326, 2246,
1510, 1267, 1100; Mass spectrometry: m/e, (relative intensity) 179 (M - , 100), 164 (70), 136 (62), 108
(17). Example 4 In the same manner as in Example 1, 2,4-dimethoxybenzonitrile was oxidized with 1 ml of 6% hydrogen peroxide in a formic acid solvent at 40°C for 2 hours, and the reaction rate was 55.
%, 3-hydroxy-2,4-dimethoxybenzonitrile yield %, selectivity 18%, 5-hydroxy-2,4-dimethoxybenzonitrile
Hydroxy-2,4-dimethoxybenzonitrile was obtained in a yield of 19% and a selectivity of 35%. Example 5 In the same manner as in Example 1, 2,6-dimethoxybenzonitrile was oxidized with 1 ml of 60% hydrogen peroxide in a formic acid solvent at 40°C for 2 hours, resulting in 3-hydroxy-2,6-dimethoxybenzo Nitrile was obtained with a reaction rate of 74%, a yield of 40%, and a selectivity of 54%. Comparative Example 1 In Example 1, when acetic acid was used as the solvent, 2,4-dimethoxybenzonitrile was
% was recovered intact.
Claims (1)
ヒドロキシ−ジメトキシベンゾニトリル化合物を
製造するにあたり、過酸化水素を酸化剤として用
いるとともに、ギ酸を溶媒及び酸化触媒として使
用することを特徴とするヒドロキシ−ジメトキシ
ベンゾニトリル化合物の製造方法。1 Oxidize the dimethoxybenzonitrile compound,
1. A method for producing a hydroxy-dimethoxybenzonitrile compound, which comprises using hydrogen peroxide as an oxidizing agent and formic acid as a solvent and an oxidation catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63291666A JPH02138165A (en) | 1988-11-18 | 1988-11-18 | Hydroxy-dimethoxybenzonitrile and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63291666A JPH02138165A (en) | 1988-11-18 | 1988-11-18 | Hydroxy-dimethoxybenzonitrile and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02138165A JPH02138165A (en) | 1990-05-28 |
| JPH0567617B2 true JPH0567617B2 (en) | 1993-09-27 |
Family
ID=17771872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63291666A Granted JPH02138165A (en) | 1988-11-18 | 1988-11-18 | Hydroxy-dimethoxybenzonitrile and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02138165A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009126784A (en) * | 2007-11-19 | 2009-06-11 | Mitsubishi Gas Chem Co Inc | A method for producing 2-iodo-3,4-dimethoxybenzonitrile. |
-
1988
- 1988-11-18 JP JP63291666A patent/JPH02138165A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02138165A (en) | 1990-05-28 |
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