JPH02138165A - Hydroxy-dimethoxybenzonitrile and its production - Google Patents
Hydroxy-dimethoxybenzonitrile and its productionInfo
- Publication number
- JPH02138165A JPH02138165A JP63291666A JP29166688A JPH02138165A JP H02138165 A JPH02138165 A JP H02138165A JP 63291666 A JP63291666 A JP 63291666A JP 29166688 A JP29166688 A JP 29166688A JP H02138165 A JPH02138165 A JP H02138165A
- Authority
- JP
- Japan
- Prior art keywords
- dimethoxybenzonitrile
- hydroxy
- compound
- hydrogen peroxide
- formulas
- 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 5
- YIEQOGHMZPTDLB-UHFFFAOYSA-N 4-hydroxy-2,3-dimethoxybenzonitrile Chemical compound COC1=C(O)C=CC(C#N)=C1OC YIEQOGHMZPTDLB-UHFFFAOYSA-N 0.000 title abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 27
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 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 abstract description 13
- 235000019253 formic acid Nutrition 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- -1 hydroxy-dimethoxybenzonitrile compound Chemical class 0.000 claims description 35
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 4
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method 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
- 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 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
- 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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-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
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000047 product Substances 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
- 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)
Abstract
Description
【発明の詳細な説明】
〔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
物及びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a hydroxy-dimethoxybenzonitrile compound and a method for producing the same.
さらに詳しくは、新規なヒドロキシ−ジメトキシベンゾ
ニトリル化合物及び、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。More specifically, it relates to a novel hydroxy-dimethoxybenzonitrile compound and a method for efficiently producing a hydroxy-dimethoxybenzonitrile compound by oxidizing the dimethoxybenzonitrile compound using formic acid as a solvent and catalyst and hydrogen peroxide as an oxidizing agent. It is something.
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（Ｌｌ 、 Ｓ 、
Ｐａｔｅｎ ｔ４．２５２．１１９３）。ところが、
これらのヒドロキシベン弓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。The 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. Also, 4-hydroxy-
3,5 dimethoxybenzonitrile has been reported to be effective as a photographic antifoggant (Ll, S,
Patent t4.252.1193). However,
Conventional methods for producing these hydroxybenzenylic nitrile compounds are difficult to obtain raw materials (reaction of hydroxy-dimethoxybenzaldehyde with hydroxylamine, Chem, Pharm, Bull, 32).
．． (1984), 4466) and the use of highly toxic cuprous cyano (Chem, Pharm, Bull.
、３２．（１９８４）、２２９６）、重金属イオンなど
の産業廃棄物を副生ずるものであった。, 32. (1984), 2296), and produced industrial waste such as heavy metal ions as by-products.
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
提供するとともに、その方法により得られる新規なヒド
ロキシ−ジメトキシベンゾニトリル化合物を提供するこ
とをその課題とする。An object of the present invention is to provide a method for industrially advantageously producing a hydroxy-dimethoxybenzonitrile compound from readily available raw materials, and to provide a novel hydroxy-dimethoxybenzonitrile compound obtained by the method. do.
そこで、本発明者は、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っ
た。Therefore, as a result of extensive research into the solvent and oxidation catalyst for producing a hydroxy-dimethoxybenzonitrile compound by oxidizing the dimethoxybenzonitrile compound with hydrogen peroxide, the present inventor found that formic acid was used as the solvent and the oxidation catalyst. It has been found that the desired hydroxy-dimethoxybenzonitrile compound can be produced in a relatively high yield by this method, and the present invention has been completed based on this finding.
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。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.
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水をギ酸溶媒中、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。The reaction method of the present invention is an extremely simple and safe oxidation method that can be easily achieved by simply mixing and stirring a dimethoxybenzonitrile compound and a hydrogen peroxide solution in a formic acid solvent under mild conditions.
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。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.
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５
０〜６０％のも２７′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。Hydrogen peroxide solutions are available in various concentrations, ranging from the commonly commercially available 30% to the higher concentration 5%.
0 to 60% of 27' can be used. 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.
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。The reaction temperature in this reaction does not require particularly strict control, but the reaction is preferably around room temperature, 0 to 100°C,
Preferably, the temperature is maintained at 10 to 70°C. The reaction time is
Although it depends on the concentration of hydrogen peroxide solution and the amount used, 1 to 24 hours is usually sufficient.
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
マトグラフィー、分別結晶などにより分離し、ＮＭＲ，
ＩＲｌ及びマススペクトルから同定し、さらに水酸基を
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。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 product is separated by column chromatography, fractional crystallization, etc., and NMR,
It was identified from IRl and mass spectra, and further confirmed by the coincidence of the above spectra between a compound with methylated hydroxyl groups and a separately synthesized standard.
本発明方法に従うと、ジメトキシベンゾニトリル化合物
からヒドロキシージメトキシベンゾニト喝ル化合物を一
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、従来法の欠陥であった産業廃
棄物を副生ず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。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 process is only water, the disadvantages of conventional methods such as generation of industrial waste as a by-product are eliminated, so this method is suitable as an industrial method for producing hydroxy-dimethoxybenzonitrile compounds. .
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。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. .
さらに、本発明によれば、下記式（１）〜（ＩＶ）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。Furthermore, according to the present invention, novel hydroxy-dimethoxybenzonitrile compounds represented by the following formulas (1) to (IV) can also be synthesized.
（Ｉ）
（■） （ＩＩＩ） （ＩＶ
）〔実施例〕
８１喉に本発明を実施例によりさらに詳細に説明する。(I) (■) (III) (IV
) [Examples] The present invention will be explained in more detail with reference to Examples.
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１０ｍ１に溶かし、３１％過酸化水素
水を２ｍ１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５０ｍ
１加え、２０ｍ１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１
０％、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。Example 1 In a glass flask, 4 mmol of 2,4-dimethoxybenzonitrile was dissolved in 10 ml of formic acid, and 2 ml of 31% hydrogen peroxide solution was added dropwise. Stirring was continued for 2 hours under a nitrogen atmosphere while maintaining the temperature at 40°C. After the reaction is complete, add 50 m of water.
1 and extracted three times with 20 ml of methylene chloride. After drying the extract with magnesium sulfate, analysis by gas chromatography revealed that 3-hydroxy-2,4-dimethoxybenzonitrile was produced in a yield of 1 at a reaction rate of 59%.
5-hydroxy-2,4-dimethoxybenzonitrile was obtained with a yield of 18% and a selectivity of 31%.
（３−ヒドロキシ−２，４−ジメトキシベンゾニトリル
）ＮＭＲ（ＣＤＣＩ３）：６３．９４（３Ｈ，Ｓ）、４
．０８（３Ｈ，Ｓ）、５．６９（ＬＨ。(3-hydroxy-2,4-dimethoxybenzonitrile) NMR (CDCI3): 63.94 (3H,S), 4
．． 08 (3H, S), 5.69 (LH.
Ｓ）、６．６５，７．１４（２１（、ＡＢｑ、Ｊ＝９Ｈ
ｚ）；ＩＲ（ＫＢｒ）：３３０４，２２２６．１６０５
，１４９９，１２９６，１２１Ｂ、１０９８．８０３（
ｃｍ−１）：質量分析：ｍ／ｅ、（相対強度＞ １７９
（Ｍ”、 １００） 、 １６４（２６） 、 １３６
（４４） 。S), 6.65, 7.14 (21(, ABq, J=9H
z);IR(KBr):3304,2226.1605
, 1499, 1296, 121B, 1098.803 (
cm-1): Mass spectrometry: m/e, (relative intensity > 179
(M”, 100), 164(26), 136
(44).
９３（２０）。93(20).
（５−ヒドロキシ−２，４−ジメトキシベンゾニトリル
）ＮＭＲ（ＣＤＣＩ、 ）：６３．９０（３Ｈ，Ｓ）
、３．９７（３Ｈ，Ｓ） 、５．３８（ＩＨ，Ｓ）、
６．５１ （ＩＨ，Ｓ） 、 ７．０７ （１）１ 、
Ｓ） ；ＩＲ（ＫＢｒ） ： ３３３４ 、２２２６．
１５２０．１２９４，１２７６．１２１４，１０２９．
８５９（ｃｍ−１）；質量分析：＋＋＋／ｅ；（相対強
度）１７９（Ｍ”、９６） 、 １６４（１００） 、
１３６（２８） 、５３（２０）。(5-hydroxy-2,4-dimethoxybenzonitrile) NMR (CDCI, ): 63.90 (3H,S)
, 3.97 (3H, S), 5.38 (IH, S),
6.51 (IH,S), 7.07 (1)1,
S); IR (KBr): 3334, 2226.
1520.1294, 1276.1214, 1029.
859 (cm-1); Mass spectrometry: +++/e; (relative intensity) 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４
０℃、２時間酸化したところ９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ルが収率１０％、選択率２９％
で得られた。Example 2 By the same method as in Example 1, 3,5-dimethoxybenzonitrile was mixed with 1 ml of 31% hydrogen peroxide solution in formic acid solvent.
After oxidation at 0°C for 2 hours, the reaction rate of 9 was 35%, and 4-hydroxy-3,5-dimethoxybenzonitrile was obtained with a yield of 4%, selectivity of 11%, and 2-hydroxy-3,5-
Dimethoxybenzonitrile yield: 10%, selectivity: 29%
Obtained with.
（２−ヒドロキシ−３，５−ジメトキシベンゾニトリル
）ＮＭＲ（ＣＤＣＩ、）：６３．８８（３Ｈ，Ｓ） 、
３．！ｌ１ｌ（３Ｈ，Ｓ） 、５．３８（ＬＨ，ｂｒ）
、６．５２（ｉｌｌ、ｄ、Ｊ＝３Ｈｚ）、６．６６（Ｉ
Ｈ，ｄ、Ｊ＝３Ｈｚ）；質量分析：ｍ／ｅ、（相対強度
）１７９（Ｍ”、 １００） 、 １６４（７３） 、
１３６（３２） 。(2-hydroxy-3,5-dimethoxybenzonitrile) NMR (CDCI, ): 63.88 (3H,S),
3. ! l1l(3H,S), 5.38(LH,br)
, 6.52 (ill, d, J=3Hz), 6.66 (I
H, d, J = 3 Hz); Mass spectrometry: m/e, (relative intensity) 179 (M”, 100), 164 (73),
136(32).
５３（２１）。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％過酸化水素水２ｍｌで４
０℃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３
９％、選択率６４％で得られた。Example 3 In the same manner as in Example 1, 2,6-dimethoxybenzonitrile was mixed with 2 ml of 31% hydrogen peroxide in formic acid solvent.
When oxidized at 0°C for 2 hours, 3-hydroxy-2,
6-dimethoxybenzonitrile reaction rate 61%, yield 3
9% and a selectivity of 64%.
（３−ヒドロキシ−２，６−ジメトキシベンゾニトリル
）ＮＭＲ（ＣＤＣ１３９：δ３．８５（３Ｈ，Ｓ）、４
．１１（３Ｈ，Ｓ） 、５．５０（ＬＨ。(3-hydroxy-2,6-dimethoxybenzonitrile) NMR (CDC139: δ3.85 (3H,S), 4
．． 11 (3H, S), 5.50 (LH.
Ｓ） 、 ６．６７、７．１０ （２Ｈ，ＡＢｑ、Ｊ＝
９Ｈｚ） ： ＩＲ（ＫＢｒ） ：３３２６．２２４６
゜１５１．０，１２６７．１１００；質量分析：ｍ／ａ
、（相対強度）１７９（阿−９１００） 、 １６４
（７０） 、 １３６（６２） 、 １０８（１７）
。S), 6.67, 7.10 (2H, ABq, J=
9Hz): IR (KBr): 3326.2246
゜151.0, 1267.1100; Mass spectrometry: m/a
, (relative intensity) 179 (A-9100) , 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６０％過酸化水素水１ｎ＋１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１０％、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３
５％で得られた。Example 4 In the same manner as in Example 1, 2,4-dimethoxybenzonitrile was oxidized with 60% hydrogen peroxide solution 1n+1 in a formic acid solvent at 40°C for 2 hours. At a reaction rate of 55%, 3-hydroxybenzonitrile -2,4-dimethoxybenzonitrile yield 10%, selectivity 18%, 5-hydroxy-2,
4-dimethoxybenzonitrile yield 19%, selectivity 3
Obtained at 5%.
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４
０℃、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。Example 5 In the same manner as in Example 1, 2,6-dimethoxybenzonitrile was mixed with 1 ml of 60% hydrogen peroxide solution in formic acid solvent.
When oxidized at 0℃ for 2 hours, 3-hydroxy-2゜6
- Dimethoxybenzonitrile reaction rate 74%, yield 40
%, with a selectivity of 54%.
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。Comparative Example 1 In Example 1, when acetic acid was used as the solvent, 2
,4-dimethoxybenzonitrile was recovered 100% intact.
Claims (2)
リル化合物。(1) The following formulas (I) to (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III ) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(IV) A novel hydroxy-dimethoxybenzonitrile compound represented by.
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。(2) A hydroxy-dimethoxybenzo compound characterized in that hydrogen peroxide is used as an oxidizing agent and formic acid is used as a solvent and an oxidation catalyst in producing a hydroxy-dimethoxybenzonitrile compound by oxidizing a dimethoxybenzonitrile compound. A method for producing a nitrile compound.
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 true JPH02138165A (en) | 1990-05-28 |
| JPH0567617B2 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) |
Cited By (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
Cited By (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. |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0567617B2 (en) | 1993-09-27 |
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