WO2007094327A1 - Méthode de synthèse d'un aldéhyde - Google Patents

Méthode de synthèse d'un aldéhyde Download PDF

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Publication number
WO2007094327A1
WO2007094327A1 PCT/JP2007/052533 JP2007052533W WO2007094327A1 WO 2007094327 A1 WO2007094327 A1 WO 2007094327A1 JP 2007052533 W JP2007052533 W JP 2007052533W WO 2007094327 A1 WO2007094327 A1 WO 2007094327A1
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Prior art keywords
autoclave
reaction
nitrogen
carbon dioxide
aldehyde
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PCT/JP2007/052533
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English (en)
Japanese (ja)
Inventor
Masaaki Yoshida
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Utsunomiya University
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Publication date
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Priority to JP2008500506A priority Critical patent/JP4852709B2/ja
Publication of WO2007094327A1 publication Critical patent/WO2007094327A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • 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
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for producing aldehydes, and more specifically, from a reaction of oxidizing a primary alcohol or an alkyl ether thereof to isolation of a product without using an organic solvent or water, and having little waste and efficiency.
  • the present invention relates to a method for producing good aldehydes.
  • Aldehydes are useful compounds as pharmaceuticals, agricultural chemicals, dyes, fragrances and other organic synthetic raw materials. Many synthetic methods have been proposed for aldehydes that are difficult to handle because they are easily oxidized.
  • Examples of methods for synthesizing corresponding aldehydes by oxidizing primary alcohol include oxidation with oxidizing agents such as chromium and manganese, Oppennauer oxidation, DMSO oxidation, Dess-Martin oxidation, TEMPO oxidation, ruthenium, etc.
  • oxidizing agents such as chromium and manganese, Oppennauer oxidation, DMSO oxidation, Dess-Martin oxidation, TEMPO oxidation, ruthenium, etc.
  • oxidizing agents such as chromium and manganese, Oppennauer oxidation, DMSO oxidation, Dess-Martin oxidation, TEMPO oxidation, ruthenium, etc.
  • oxidizing agents such as chromium and manganese, Oppennauer oxidation, DMSO oxidation, Dess-Martin oxidation, TEMPO oxidation, ruthenium, etc.
  • acid oxides of these transition metal catalysts Non-pat
  • Patent Document 1 a method using a halogen oxide as an oxidizing agent has been developed.
  • these are expensive catalysts, and it is necessary to treat a harmful metal compound remaining after the reaction is completed. Or a large amount of waste is generated, resulting in a production method with a large E-factor (ratio of waste to product: Non-Patent Document 3), which is not an environmentally and economically preferable production method. .
  • Nitric acid-nitrogen is a raw material for nitric acid, and is therefore an inexpensive oxidant following oxygen.
  • diacid-nitrogen is strong in acidity, there is an economical method for diluting with an organic solvent and acidifying a primary alcohol to obtain an aldehyde (for example, Patent Documents 2 and 3, Non-patent Documents). Four).
  • An organic solvent has been used as a reaction medium for the oxidation reaction so far, but the oxidant is not only a substrate but also a part of the organic solvent may be oxidized, and the oxidant is wasted. Not only when As a result, a runaway reaction may occur. For this reason, when an oxidizing agent having a large oxidizing power such as nitrogen dioxide is used, a solvent inert to an oxidizing agent such as tetrasalt carbon, carbon form, and 1,2-dichloroethane has been used. . However, such chlorinated solvents have many problems in toxicity and disposal, and are not necessarily preferred as reaction media.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2004-43317
  • Patent Document 2 Japanese Patent Laid-Open No. 2002-179607
  • Patent Document 3 Japanese Patent No. 3371544
  • Non-specialty literature 1 Green Chemistry: Theory and Practice, Oxford University Press, 19 98
  • Non-Patent Document 2 Chemical Society of Japan, Experimental Chemistry Course, Synthesis of Organic Compounds m-Aldehyde 'Keton' Quinone, 5th Edition, Maruzen Co., Ltd., 2003, 15 ⁇ , pages 9-44
  • Non-Patent Document 3 R. A. Sheldon, Chem. Ind., 7, 903 (1992)
  • Non-Patent Document 4 B. 0. Field, J. Grundy, J. Chem. Soc., 1955, 1110—1112.
  • the problem of the present invention is that safety can be taken into account in an acid-oxidation reaction, and the yield and purity of aldehydes that are easily oxidized are not reduced in isolation and purification. And low waste! It is to provide a comprehensive environmentally friendly aldehyde production method.
  • the invention of claim 1 adds nitrogen dioxide or nitrogen tetraoxide to primary alcohol or alkyl ether thereof together with diacid-carbon in a gaseous state, liquid state, or supercritical state. It is a method for producing aldehydes characterized by reacting [0013] According to the invention of claim 2, a high purity aldehyde can be obtained by removing the remaining dinitrogen tetroxide or tehyniform nitrogen and their ring isomers with carbon dioxide after the reaction.
  • FIG. 1 Graph showing the relationship between the mixing ratio of diacid-carbon to diacid-nitrogen and the yield of 4-methylbenzaldehyde.
  • Examples of the primary alcohol used in the present invention include compounds in which an alcohol residue is bonded to an aromatic ring or a heterocyclic ring as a hydroxymethyl group, and those bonded to an aliphatic skeleton as a hydroxyl group.
  • aromatic primary alcohol examples include aromatic compounds having one or more hydroxymethyl groups on the heterocycle, such as benzyl alcohol, hydroxymethylnaphthalene, furfuryl alcohol, Hydroxymethyl pyridine, hydroxymethyl quinoline, benzene dimethanol, dihydroxymethyl biphenyl, etc.
  • the aromatic ring or heterocycle hydrogen is an alkyl group, a cycloalkyl group, an aryl group, an alkyl group, an alkyl group.
  • It may be substituted with a group, an aralkyl group, a hydroxyl group, a halogen, a nitro group, an amino group, an alkoxy group, an alkylamino group, a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, or the like.
  • the aliphatic primary alcohols include monovalents such as ethanol, propanol, 2-methylpropanol, butanol, hexanol, heptanol, octanol, 2-ethinohexanol, decanol, dodecanol, stearyl alcohol and the like.
  • Alcohols ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, trimethylololeethane, pentaerythritol, dipentaerythritol, gnole
  • polyhydric alcohols such as course, sorbitol, starch, and polybulal alcohol.
  • the alkyl ether of the primary alcohol is obtained by replacing the hydrogen of the hydroxyl group of the primary alcohol with an alkyl group (1 to 4 carbon atoms).
  • reaction conditions for efficiently and selectively obtaining an aldehyde mainly by adjusting the mixing ratio of diacid-carbon and diacid-nitrogen and the reaction temperature.
  • the amount of nitrogen dioxide used is about 0.1 to 10 moles, preferably 0.8 to 3 moles, more preferably about 1.0 to 1.3 moles per mole of substrate of an alcohol residue or one alkyl ether residue thereof. .
  • reaction rate When highly reactive nitrogen dioxide is diluted with carbon dioxide, the reaction rate can be controlled and it becomes easy to handle.
  • Diacid-nitrogen is in equilibrium with tetraacid-nitrogen. Increasing the temperature tilts the equilibrium toward the more reactive diacid-nitrogen side, but when pressure is applied, it can tilt toward the more moderately reactive tetraacid-nitrogen side. By controlling the pressure with carbon, the equilibrium can be controlled and the reactivity of nitrogen dioxide can be controlled.
  • the mixing ratio of diacid-carbon to diacid-nitrogen can be appropriately selected depending on the type of substrate, for example, 1 to 1000 times, preferably 10 to 200 times, more preferably 30 to 100 times. It is about double.
  • the reaction temperature can be appropriately selected depending on the kind of the substrate, and is, for example, about -50 to 150 ° C, preferably -20 to 120 ° C, and more preferably about 0 to 50 ° C. If the temperature is too high, the oxidation proceeds further and the corresponding carboxylic acid is likely to be produced.
  • Nitric acid dinitrogen or quaternary nitric acid, their ring element, and dioxygen carbon are gases at normal temperature and pressure, so that the product can be easily obtained by opening the valve of the sealed container after the reaction. And can be separated.
  • Diacid-nitrogen dissolves very well in liquid or supercritical diacid-carbon. Therefore, the excess diacid nitrogen or tetraacid nitrogen and their ring elements existing after the reaction can be removed together with the diacid carbon when the reaction vessel valve is opened. Furthermore, extraction and removal are also easy by circulating carbon dioxide in the reaction vessel.
  • a ring element such as monoacid-nitrogen produced after the reaction can be easily regenerated to diacid-nitrogen by acidification with oxygen. Therefore, it can be recycled with the carbon dioxide used.
  • the autoclave is cooled with ice and depressurized, and then the remaining nitrogen dioxide or tetranitrogen tetroxide and their cyclic compounds are removed with carbon dioxide.
  • the contents were analyzed by gas chromatography using decane as an internal standard.
  • Example 2 ⁇ Examination of mixing ratio of carbon dioxide to nitrogen dioxide> In a 50 ml stainless steel autoclave, weigh 0.19 g (4.1 mol) of nitrogen dioxide at room temperature, then add a predetermined amount of liquid phosphonic acid and carbon at room temperature and mix well.
  • the autoclave is cooled with ice and depressurized, and then the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide.
  • the reaction vessel was opened and the yield of 4 methylbenzaldehyde was quantified by gas chromatography.
  • the autoclave After the reaction, the autoclave is cooled with ice and depressurized. Then, the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide. The contents and the reaction mixture were analyzed by 1 H NMR using coumarin as an internal standard.
  • Nitrogen dioxide 0.18 g (3.9 mmol) and 4-methoxybenzyl alcohol (0.47 g, 3.4 mmol) are weighed into a 50 ml stainless steel autoclave that has been purged with argon and cooled.
  • This autoclave was placed in a 25 ° C water bath and stirred for 1 hour with a magnetic stirrer.
  • the autoclave is ice-cooled, and then the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide.
  • the contents of the reaction mixture were analyzed by 1 H NMR using coumarin as an internal standard.
  • the autoclave is cooled with ice and depressurized, and the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide.
  • the reaction vessel was opened and the reaction mixture was analyzed by gas chromatography using decane as an internal standard.
  • the autoclave is cooled with ice and depressurized, and then the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide.
  • the reaction vessel was opened and the reaction mixture was analyzed by gas chromatography using decane as an internal standard.
  • the autoclave is cooled with ice and depressurized, and then the remaining nitrogen dioxide or dinitrogen tetroxide and their ring elements are removed with carbon dioxide.
  • the reaction vessel was opened and the reaction mixture was analyzed by gas chromatography using decane as an internal standard.
  • valve Operate the valve to transfer the contents to an autoclave containing benzyl methyl ether.
  • the pressure was 5.9 MPa. The reaction was stirred for 1 hour with a magnetic stirrer.
  • the autoclave is cooled with ice and depressurized. Then, the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide. The contents were analyzed by gas chromatography using decane as an internal standard.
  • the autoclave is cooled with ice and depressurized. Then, the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide. The contents were analyzed by gas chromatography using decane as an internal standard.
  • Nitrogen dioxide is weighed into a 50 ml stainless steel autoclave at 0.31 g (6.7 mmol) at room temperature, followed by liquid oxalate and carbon at 10.25 g at room temperature and mixed well.
  • the autoclave is cooled with ice and depressurized. Then, the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide. The contents were analyzed by gas chromatography using decane as an internal standard.
  • the autoclave is cooled with ice and depressurized, and the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide.
  • the contents were analyzed by gas chromatography using decane as an internal standard.
  • the autoclave is cooled with ice and depressurized, and then the remaining nitrogen dioxide or dinitrogen tetroxide and their cyclic compounds are removed with carbon dioxide.
  • the contents were analyzed and quantified by 1 H NMR using coumarin as an internal standard, and the purity was confirmed by gas chromatography.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention a pour objet une méthode d'isolement d'un aldéhyde de façon stable et une méthode générant une quantité réduite de déchets au cours du procédé de synthèse d'un aldéhyde par oxydation de l'alcool primaire correspondant ou de son éther alkylique. La présente invention a pour objet une méthode de production d'un aldéhyde caractérisée en ce qu'elle comprend une réaction d'addition de dioxyde d'azote ou de tétroxyde de diazote et de dioxyde de carbone à l'état gazeux, liquide ou supercritique avec un alcool primaire ou son ester alkylique. Dans un mode d'application préféré, le dioxyde d'azote ou le tétroxyde de diazote restant après la réaction décrite ci-dessus, ainsi que les produits de réduction desdits composés, sont éliminés à l'aide de dioxyde de carbone pour obtenir un aldéhyde de pureté élevée.
PCT/JP2007/052533 2006-02-13 2007-02-13 Méthode de synthèse d'un aldéhyde WO2007094327A1 (fr)

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JP2008500506A JP4852709B2 (ja) 2006-02-13 2007-02-13 アルデヒド類の製造方法

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JP2006-035394 2006-12-25

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07330655A (ja) * 1994-06-10 1995-12-19 Ube Ind Ltd 芳香族アルデヒドの製造方法
US5831116A (en) * 1996-12-18 1998-11-03 Northeastern University Catalytic process for making ethers, aldehydes esters and acids from alcohols using a supercritical fluid mobile
JPH1135511A (ja) * 1997-07-22 1999-02-09 Ube Ind Ltd 芳香族アルデヒドの製造方法
JP2000016959A (ja) * 1998-07-01 2000-01-18 Mitsui Chemicals Inc メタクロレインの製造方法
JP2002179607A (ja) * 2000-12-14 2002-06-26 Daicel Chem Ind Ltd フタルアルデヒド類の製造方法
JP2002212334A (ja) * 2000-10-31 2002-07-31 Masaaki Yoshida 高分子物質の破壊方法及び化学原料化法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4097316B2 (ja) * 1998-03-04 2008-06-11 ダイセル化学工業株式会社 エーテル類の酸化方法、及びアセタール化合物又はカルボニル化合物の製造法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07330655A (ja) * 1994-06-10 1995-12-19 Ube Ind Ltd 芳香族アルデヒドの製造方法
US5831116A (en) * 1996-12-18 1998-11-03 Northeastern University Catalytic process for making ethers, aldehydes esters and acids from alcohols using a supercritical fluid mobile
JPH1135511A (ja) * 1997-07-22 1999-02-09 Ube Ind Ltd 芳香族アルデヒドの製造方法
JP2000016959A (ja) * 1998-07-01 2000-01-18 Mitsui Chemicals Inc メタクロレインの製造方法
JP2002212334A (ja) * 2000-10-31 2002-07-31 Masaaki Yoshida 高分子物質の破壊方法及び化学原料化法
JP2002179607A (ja) * 2000-12-14 2002-06-26 Daicel Chem Ind Ltd フタルアルデヒド類の製造方法

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JP4852709B2 (ja) 2012-01-11

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