WO2007094327A1

WO2007094327A1 - Method of producing aldehyde

Info

Publication number: WO2007094327A1
Application number: PCT/JP2007/052533
Authority: WO
Inventors: Masaaki Yoshida
Original assignee: Utsunomiya University
Priority date: 2006-02-13
Filing date: 2007-02-13
Publication date: 2007-08-23
Also published as: JP4852709B2; JPWO2007094327A1

Abstract

[PROBLEMS] To provide a method of stably isolating an aldehyde and a method accompanied by the generation of waste in a reduced amount in the process of producing an aldehyde by oxidizing the corresponding primary alcohol or its alkyl ether. [MEANS FOR SOLVING PROBLEMS] A method of producing an aldehyde characterized by comprising conducting a reaction by adding nitrogen dioxide or dinitrogen tetroxide together with carbon dioxide in the gaseous, liquid or supercritical state to a primary alcohol or its alkyl ester. In a preferable embodiment, nitrogen dioxide or dinitrogen tetroxide remaining after the completion of the reaction as described above and reduced compounds thereof are purged with carbon dioxide to thereby give an aldehyde at a high purity.

Description

Specification

Method for producing aldehydes

Technical field

[0001] 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.

Background art

[0002] In the 21st century society aiming for sustainable development, when producing useful compounds, it is required to be a comprehensive environmentally friendly manufacturing method called green chemistry (for example, Non-patent document 1).

[0003] 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.

[0004] 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. There are known acid oxides of these transition metal catalysts (Non-patent Document 2).

[0005] Also, a method using a halogen oxide as an oxidizing agent has been developed (Patent Document 1). However, 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. .

[0006] Nitric acid-nitrogen is a raw material for nitric acid, and is therefore an inexpensive oxidant following oxygen. However, since 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).

[0007] 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.

[0008] In addition, after conventional aldehyde synthesis reaction, force that has been worked up such as washing, concentration of solvent, distillation of aldehyde, etc. Aldehyde is oxidized and immediately becomes part of carboxylic acid during these treatments. As a result, the yield and purity of the aldehyde may be reduced. 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 卷, 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.

Disclosure of the invention

Problems to be solved by the invention

[0009] Therefore, 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.

[0010] Another subject of the present invention will become apparent from the following description.

Means for solving the problem

[0011] As a result of intensive investigations into a comprehensive environmentally friendly aldehyde production method, the present inventors have completed the following inventions.

[0012] 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. The method for producing aldehydes according to claim 1, wherein:

The invention's effect

[0014] According to the present invention, it is possible to give consideration to the safety of the acid-acid reaction, and in the isolation and purification, the yield and purity of aldehydes that are easily oxidized are not reduced, and they are economical and have little waste. ! / ヽ, we can provide a comprehensive environment-friendly aldehyde production method.

Brief Description of Drawings

[0015] [Fig. 1] Graph showing the relationship between the mixing ratio of diacid-carbon to diacid-nitrogen and the yield of 4-methylbenzaldehyde.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] 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.

[0017] Specific examples of the aromatic primary alcohol 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.

[0018] In addition, 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 Examples thereof include polyhydric alcohols such as course, sorbitol, starch, and polybulal alcohol.

[0019] 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).

[0020] In the present invention, it is possible to select 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.

[0021] 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. .

[0022] When highly reactive nitrogen dioxide is diluted with carbon dioxide, the reaction rate can be controlled and it becomes easy to handle.

[0023] 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.

[0024] [Chemical 1]

[0025] 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.

[0026] 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. [0027] 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.

[0028] 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.

[0029] Further, 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. Example

[0030] Hereinafter, the present invention is not limited by the powerful examples for describing the embodiments of the present invention.

[0031] Example 1

Weigh 0.15 g (3.3 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add 10.0 g of liquid phosphonic acid carbon at room temperature and mix well.

[0032] With a pressure gauge! In a separate 50 ml stainless steel autoclave, weigh 4-methylbenzylalcohol monole (0.37 g, 3.0 mmol), replace the autoclave with carbon dioxide, and cool well. Connect to the autoclave with nitric acid and nitrogen.

[0033] Operate the valve to transfer the contents to an autoclave containing 4-methylbenzyl alcohol.

[0034] When this autoclave was placed in a 40 ° C water bath, the pressure became 5.6 MPa. The reaction was stirred for 1 hour with a magnetic stirrer.

[0035] After the reaction, 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.

As a result, 0.36 g (yield 100%) of 4-methylbenzaldehyde was obtained, and the purity was 99.2%.

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.

[0038] With a pressure gauge! In a separate 50 ml stainless steel autoclave, weigh 4-methylbenzyl alcohol monole (0.37 g, 3.0 mmol), replace the autoclave with carbon dioxide, and cool well. Connect to the autoclave with nitric acid and nitrogen.

[0039] Operate the valve to transfer the contents to an autoclave containing 4-methylbenzyl alcohol. This autoclave was placed in a 25 ° C. water bath, and reacted with stirring with a magnetic stirrer for 1 hour.

[0040] After the reaction, 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.

[0041] By performing the same operation while changing the amount of carbon dioxide to be added, the relationship between the mixing ratio of diacid carbon to dioxygen nitrogen and the yield of 4-methylbenzaldehyde was investigated. Figure 1 shows the result.

[0042] Example 3

Weigh 0.22 g (4.8 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add liquid oxalic acid carbon at 9.92 g at room temperature and mix well.

[0043] Attach a pressure gauge! To another 50 ml stainless steel autoclave, weigh 4-methoxybenzyl alcohol (0.44 g, 3.4 mmol), replace the autoclave with carbon dioxide, and cool well. Connect with the previous autoclave containing acid and nitrogen.

[0044] Operate the valve to transfer the contents to an autoclave containing 4-methoxybenzyl alcohol.

[0045] When this autoclave was placed in a 25 ° C water bath, the pressure became 5.2 MPa. The reaction was stirred for 1 hour with a magnetic stirrer.

[0046] 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.

As a result, 0.43 g (yield 100%) of 4-methoxybenzaldehyde was obtained. [0048] Comparative Example 1

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.

[0049] This autoclave was placed in a 25 ° C water bath and stirred for 1 hour with a magnetic stirrer.

[0050] After the reaction, 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.

As a result, 0.42 g (yield 91%) of 4-methoxybenzaldehyde and 0.2 g (yield 3%) of 4-methoxybenzoic acid were obtained.

[0052] Example 4

Weigh 0.17 g (3.7 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add 9.43 g of liquid silicate and carbon at room temperature and mix well.

[0053] In a separate 50 ml stainless steel autoclave equipped with a pressure gauge, add benzyl alcohol (0.3

2 g, 3.0 mmol), replace the autoclave with carbon dioxide and cool well.

Connect to the autoclave with nitric acid and nitrogen.

[0054] The contents are transferred to an autoclave containing benzyl alcohol by operating the valve. When this autoclave was placed in a 35 ° C water bath, the pressure became 5.2 MPa. The reaction was stirred for 1 hour with a magnetic stirrer.

[0055] After the reaction, 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.

As a result, 0.31 g (yield 98%) of benzaldehyde was obtained.

[0057] Example 5

Weigh 0.12 g (3.5 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add liquid oxalic acid carbon at 9.87 g at room temperature and mix well.

[0058] In a separate 50 ml stainless steel autoclave equipped with a pressure gauge, weigh 3-nitrobenzyl alcohol monole (0.46 g, 3.0 mmol) and replace the autoclave with carbon dioxide. Cool and connect to the autoclave with nitric acid and nitrogen.

[0059] Operate the valve to transfer the contents to an autoclave containing 3-trobensyl alcohol. When this autoclave was placed in a 40 ° C water bath, the pressure became 5.1 MPa. The reaction was stirred with a magnetic stirrer for 2 hours.

[0060] After the reaction, 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.

As a result, 0.45 g (99% yield) of 3-nitrobenzaldehyde was obtained.

[0062] Example 6

Weigh 0.12 g (3.5 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add 5.50 g of liquid carbonic acid carbon at room temperature and mix well.

[0063] With a pressure gauge! In a separate 50 ml stainless steel autoclave, weigh 4_ black benzyl alcohol (0.435 g, 3.1 mmol), replace the autoclave with carbon dioxide, and cool well. Connect to the autoclave with nitric acid and nitrogen.

[0064] Move the contents to an autoclave containing 4-clonal benzyl alcohol by operating the valve. When this autoclave was placed in a 40 ° C water bath, the pressure became 3.9 MPa. The reaction was stirred with a magnetic stirrer for 2 hours.

[0065] After the reaction, 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.

As a result, 0.42 g (yield 98%) of 4-clonal benzaldehyde was obtained.

[0067] Example 7

Weigh 0.33 g (7.2 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add liquid phosphonic acid carbon at 10.71 g at room temperature and mix well.

[0068] In a separate 50 ml stainless steel autoclave equipped with a pressure gauge, add benzyl methyl ether.

Weigh out (0.35 g, 3.1 mmol), replace this autoclave with diacid-carbon, cool well, and connect to the autoclave containing diacid-nitrogen.

[0069] Operate the valve to transfer the contents to an autoclave containing benzyl methyl ether. [0070] When the autoclave was placed in a water bath at 45 ° C, the pressure was 5.9 MPa. The reaction was stirred for 1 hour with a magnetic stirrer.

[0071] 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 were analyzed by gas chromatography using decane as an internal standard.

As a result, 0.32 g (yield 98%) of benzaldehyde was obtained.

[0073] Example 8

Weigh 0.12 g (3.9 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add liquid oxalic acid carbon at 8.85 g at room temperature and mix well.

[0074] In a separate 50 ml stainless steel autoclave equipped with a pressure gauge, weigh 3-methylbenzylalcohol monole (0.38 g, 3.1 mmol), replace the autoclave with carbon dioxide, and cool well. Connect with the previous autoclave containing acid and nitrogen.

[0075] Operate the valve to transfer the contents to an autoclave containing 3-methylbenzyl alcohol.

[0076] When this autoclave was placed in a 25 ° C water bath, the pressure became 4.8 MPa. The reaction was stirred for 1 hour with a magnetic stirrer.

[0077] 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 were analyzed by gas chromatography using decane as an internal standard.

As a result, 0.37 g (99% yield) of 3-methylbenzaldehyde was obtained.

[0079] Example 9

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.

[0080] In a separate 50 ml stainless steel autoclave equipped with a pressure gauge, weigh 2-methylbenzylalcohol monole (0.37 g, 3.0 mmol), replace the autoclave with carbon dioxide, and cool well. Connect with the previous autoclave containing acid and nitrogen.

[0081] Operate the valve to put the contents into an autoclave containing 2-methylbenzyl alcohol. Transfer.

[0082] When the autoclave was placed in a 25 ° C water bath, the pressure became 5.2 MPa. The reaction was stirred for 1 hour with a magnetic stirrer.

[0083] 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 were analyzed by gas chromatography using decane as an internal standard.

As a result, 0.36 g (yield 98%) of 2-methylbenzaldehyde was obtained.

[0085] Example 10

Weigh out 0.18 g (3.9 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add 5.62 g of liquid carbonic acid carbon at room temperature and mix well.

[0086] In a separate 50 ml stainless steel autoclave equipped with a pressure gauge, weigh 3-bromobenzylalcohol monole (0.58 g, 3.1 mmol), replace the autoclave with carbon dioxide, and cool well. Connect with the previous autoclave containing acid and nitrogen.

[0087] Operate the valve to transfer the contents to the autoclave containing 3-bromobenzyl alcohol.

[0088] When the autoclave was placed in a water bath at 40 ° C, the pressure became 3.8 MPa. The reaction was stirred for 3 hours with a magnetic stirrer.

[0089] After the reaction, 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.

As a result, 0.57 g (99% yield) of 3-bromobenzaldehyde was obtained.

[0091] Example 11

Weigh 0.15 g (3.3 mmol) of nitrogen dioxide in a 50 ml stainless steel autoclave at room temperature, then add liquid phosphonic acid carbon at 6.16 g at room temperature and mix well.

[0092] In a separate 50 ml stainless steel autoclave equipped with a pressure gauge, weigh 1,4-benzenedimethanol (0.21 g, 1.5 mmol), replace the autoclave with carbon dioxide, and cool well. Connect with the previous autoclave containing acid and nitrogen.

[0093] Operate the valve to transfer the contents to the autoclave containing 1,4-benzenedimethanol. The

[0094] When the autoclave was placed in a 25 ° C water bath, the pressure was 3.9 MPa. The reaction was stirred for 1 hour with a magnetic stirrer.

[0095] After the reaction, 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.

As a result, 0.20 g (yield 98%, purity 99.8%) of 1,4-benzenedialdehyde was obtained.

Claims

The scope of the claims

[1] Aldehydes characterized by reacting primary alcohol or its alkyl ether with nitrogen dioxide tetraacid or nitrogen tetraoxide together with carbon dioxide in a gaseous state, liquid state or supercritical state Manufacturing method.

[2] The high-purity aldehyde is obtained by removing residual diacid-nitrogen or tetraacid-nitrogen and their ring elements with carbon dioxide after the reaction. The method for producing aldehydes according to 1.