CN101318885B - Preparation method for converting organic carboxylic acid into organic aldehyde - Google Patents
Preparation method for converting organic carboxylic acid into organic aldehyde Download PDFInfo
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- CN101318885B CN101318885B CN2008100171616A CN200810017161A CN101318885B CN 101318885 B CN101318885 B CN 101318885B CN 2008100171616 A CN2008100171616 A CN 2008100171616A CN 200810017161 A CN200810017161 A CN 200810017161A CN 101318885 B CN101318885 B CN 101318885B
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Abstract
The invention relates to organic synthesis, in particular to a preparation method for converting an organic carboxylic acid to an organic aldehyde. The method comprises the steps that: two reactions are carried out in a reaction container to convert a carboxyl in a carboxylic acid to a boroxyl compound first and then to oxidize the boroxyl compound to an aldehyde by an acetone solution of a trichloroisocyanuric acid with a mass 1.0 to 1.2 times that of the reaction substrate of carboxylic acid at a temperature of between 0 and 40 DEG C in the presence of 0.1 to 1.0 percent of 2,2,6,6-tetramethylpiperidine-1-oxyl against the mass of the reaction substrate of carboxylic acid and a base with a mass 1.0 to 1.2 times that of the reaction substrate of carboxylic acid. The method for preparing the aldehyde from the organic carboxylic acid by one-pot reaction of the invention has the advantages of moderate reaction conditions, rapid reaction, green reaction due to use of nontoxic oxidizer, simple process, easy operation, easy handling, and contribution to the realization of industrialization.
Description
Technical field
The present invention relates to organic synthetic, a kind of specifically preparation method who organic carboxyl acid is converted into organic aldehyde.
Background technology
Aldehyde is the very important compound of a class in the organic synthesis, in industries such as petrochemical complex, fine chemistry industry and medicine important use is arranged.Generally speaking, aldehyde is difficult to directly to reduce preparation by carboxylic acid, because aldehyde is reduced (chemistry is circulated a notice of, 2002) than carboxylic acid is easier.
HC Brown has reported by the carboxylic acid reduction and has reoxidized the method (Synthesis that two steps prepared aldehyde, 1979), the weak point of this method has been to use in oxidising process pyridine-chromic salt this price not only expensive but also the reagent of severe toxicity arranged, and reaction product aftertreatment difficulty, seriously polluted, the entire reaction course yield is not high, and its industrial application is restricted.
Summary of the invention
The purpose of this invention is to provide a kind of reaction conditions gentleness, be swift in response, technology is simple, easy to operate, easily separated, uses nontoxic oxygenant, adopts the preparation method who organic carboxyl acid is converted into organic aldehyde of one pot reaction.
For achieving the above object, the technical solution used in the present invention is:
Organic carboxyl acid is converted into the preparation method of organic aldehyde: in same reactor through two-step reaction, earlier the carboxyl in the carboxylic acid is converted into oxygen boryl compound, add quality then and be reaction substrate carboxylic acid quality 0.1%-1.0% 2,2,6,6-tetramethyl piperidine oxide compound (TEMPO) and the normal 1.0-1.2 of reaction substrate carboxylic acid alkali doubly, the acetone soln with the normal 1.0-1.2 of reaction substrate carboxylic acid TCCA (Trichloroisocyanuric acid) (TCCA) doubly under 0-40 ℃ is oxidized to aldehyde.
Described carboxyl in the carboxylic acid is converted into oxygen boryl compound for being dissolved in the 60mmol carboxylic acid in anhydrous diethyl ether or the tetrahydrofuran (THF) and following stirring, normal temperature drips 60-66mmol borine-dimethyl thioether down, dropwising the back refluxes, after removing anhydrous diethyl ether or tetrahydrofuran (THF), the methylene dichloride or the acetone that add 150-200ml again, obtain the methylene dichloride or the acetone soln of oxygen boryl compound, stand-by.Described backflow 1-2 hour.The acetone soln of described TCCA (Trichloroisocyanuric acid) TCCA is added drop-wise in the reaction solution and stirs; Reacted stopped reaction after dropwising again 1-2 hour.Reaction adds saturated NH with product after finishing
4The Cl aqueous solution is used dichloromethane extraction, and drying is removed and desolvated, and makes to obtain product purification.Described carboxylic acid is lipid acid and substituted fatty acid or aromatic acid and substituted aroma acid thereof.Described lipid acid and substituted fatty acid are suc as formula shown in down:
R1 is-CH
3, Cl, Br, CO
2CH
3, CO
2C
2H
5N=3-10.Described aromatic acid and substituted aroma acid thereof are suc as formula shown in down:
R2＝H、F、Cl、Br、NO
2、CN、COCH
3、CO
2CH
3、CO
2CH
2CH
3。Described alkali is yellow soda ash, sodium bicarbonate, pyridine, picoline or triethylamine.
The advantage that the present invention had: the one pot reaction that the present invention adopts prepares the method for aldehyde by organic carboxyl acid, the reaction conditions gentleness, is swift in response, and uses nontoxic oxygenant, the reaction process green, and simple, easy to operate, the easy processing of technology helps realizing industrialization.
Embodiment
Following examples are to further specify of the present invention, but the invention is not restricted to this.
1) carboxylic acid is dissolved in anhydrous diethyl ether or the tetrahydrofuran (THF), vigorous stirring, normal temperature drips borine-dimethyl thioether down, dropwises the back and refluxes 1 hour.Remove anhydrous diethyl ether or tetrahydrofuran (THF), add methylene dichloride or acetone again, obtain the methylene dichloride or the acetone soln of oxygen boryl compound.
2) in the methylene dichloride of oxygen boryl compound or acetone soln, add the TEMPO and the stoichiometric yellow soda ash of catalytic amount, under 0-40 ℃, drip the acetone soln of TCCA (20mmol) and stir; React 30min, stopped reaction after dropwising again.Add 30ml NH
4The Cl saturated aqueous solution is used dichloromethane extraction, and drying is removed and desolvated, and obtains product.
Embodiment 1
The preparation of n-octaldehyde: 1) in the dry there-necked flask of 250ml, add n-caprylic acid 9.5ml (60mmol) and 100ml anhydrous diethyl ether, vigorous stirring, normal temperature drips borine-dimethyl thioether 6.12ml (60mmol) down, dropwises the back and refluxes 1 hour.Stopped reaction is removed anhydrous diethyl ether, adds 50ml acetone again, obtains the acetone soln of oxygen boryl compound.2) in the acetone soln of 50ml oxygen boryl compound, add TEMPO and the 6.4g yellow soda ash of 0.01g, under 25 ℃, Dropwise 5 0ML contain 5.1g TCCA (22mmol) TCCA acetone soln and stir; React 30min, stopped reaction after dropwising again.Add water 30ml NH
4The Cl saturated aqueous solution is used 150ml dichloromethane extraction three times, and drying is removed and desolvated, and obtains product 7.4g, productive rate 96%.
Embodiment 2
Difference from Example 1 is, the preparation of 9-acyloxy pelargonic acid methyl esters: 9-methoxyl group-9-acyloxy pelargonic acid 12.1g (60mmol) is dissolved in the tetrahydrofuran solution, normal temperature drips borine-dimethyl thioether 6.12ml (60mmol), adds the 150ml methylene dichloride again, obtains the dichloromethane solution of oxygen boryl compound.Then add 0.05gTEMPO and 5.8g pyridine again, contain at 0 ℃ of following Dropwise 5 0ML and react 60min again, stopped reaction after the acetone soln of 5.6g TCCA and agitation and dropping finish.Promptly make target product, productive rate 98%.
Embodiment 3
Difference from Example 1 is, the preparation of 4-chloro-benzaldehyde: Chlorodracylic acid 9.4g (60mmol) is dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the anhydrous ether solution, add 50ml acetone again, obtain the acetone soln of oxygen boryl compound.Then add again 0.02gTEMPO and and the 7.0g picoline, drip down 100ML at 5 ℃ and contain the acetone soln of 6.0g TCCA and stir, react 60min after dropwising again, stopped reaction.Promptly make target product, productive rate 96%.
Embodiment 4
Difference from Example 1 is, the preparation of paranitrobenzaldehyde: p-nitrobenzoic acid 10g (60mmol) is dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the tetrahydrofuran solution, add the 30ml methylene dichloride again, obtain the dichloromethane solution of oxygen boryl compound.Then add again 0.01g TEMPO and and the 5.0g sodium bicarbonate, drip down 100ml at 10 ℃ and contain the acetone soln of 6.0g TCCA and stir, react 60min after dropwising again, stopped reaction.Promptly make target product, productive rate 90%.
Embodiment 5
Difference from Example 1 is, the preparation of aubepine: anisic acid 9.1g (60mmol) is dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the anhydrous ether solution, add 30ml acetone again, obtain the acetone soln of oxygen boryl compound.Then add 0.05g TEMPO and 7.5g triethylamine again, drip acetone soln and the stirring that 100ml contains 6.0g TCCA down, react 60min after dropwising again, stopped reaction at 12 ℃.Promptly make target product, productive rate 95%.
Embodiment 6
Difference from Example 1 is; preparation to the aldehyde radical methyl phenyl ketone: will be dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the tetrahydrofuran solution to acetylbenzoic acid 9.8g (60mmol); add the 50ml methylene dichloride again, obtain the dichloromethane solution of oxygen boryl compound.Then add 0.01g TEMPO and 7g yellow soda ash again, drip acetone soln and the stirring that 100ml contains 6.0g TCCA down, react 60min after dropwising again, stopped reaction at 15 ℃.Promptly make target product, productive rate 89%.
Embodiment 7
Difference from Example 1 is, the preparation of terephthalaldehydic acid ethyl ester: will be dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the anhydrous ether solution to carboxyl ethyl benzoate 11.6g (60mmol), add 50ml acetone again, obtain the acetone soln of oxygen boryl compound.Then add again 0.05g TEMPO and and 7g yellow soda ash, drip down 100ml at 25 ℃ and contain the acetone soln of 6.0g TCCA and stir, react 60min after dropwising again, stopped reaction.Promptly make target product, productive rate 94%.
Embodiment 8
Difference from Example 1 is, preparation to phenyl aldehyde: phenylformic acid 7.3g (60mmol) is dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the tetrahydrofuran solution, add the 50ml methylene dichloride again, obtain the dichloromethane solution of oxygen boryl compound.Then add again 0.05gTEMPO and and 7g yellow soda ash, drip down 100ml at 25 ℃ and contain the acetone soln of 6.0g TCCA and stir, react 60min after dropwising again, stopped reaction.Promptly make target product, productive rate 98%.
Embodiment 9
Difference from Example 1 is, between the preparation of tolyl aldehyde: m-methyl benzoic acid 8.2g (60mmol) is dissolved in normal temperature drips 6.6ml (65mmol) borine-dimethyl thioether in the anhydrous ether solution, add 50ml acetone again, obtain the acetone soln of oxygen boryl compound.Then add again 0.02gTEMPO and and 7g yellow soda ash, drip down 100ml at 20 ℃ and contain the acetone soln of 6.0g TCCA and stir, react 60min after dropwising again, stopped reaction.Promptly make target product, productive rate 96%.
Embodiment 10
Difference from Example 1 is, between the preparation of cyanobenzaldehyde: m-cyanobenzoic acid 8.86g (60mmol) is dissolved in normal temperature drips 6.6ml (65mmol) borine-dimethyl thioether in the tetrahydrofuran solution, add the 50ml methylene dichloride again, obtain the dichloromethane solution of oxygen boryl compound.Then add again 0.01g TEMPO and and 7g yellow soda ash, drip down 100ml at 25 ℃ and contain the acetone soln of 6.0g TCCA and stir, react 60min after dropwising again, stopped reaction.Promptly make target product, productive rate 94%.
Embodiment 11
Difference from Example 1 is, the preparation of phenoxy acetaldehyde: phenylium 9.1g (60mmol) is dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the anhydrous ether solution, add 50ml acetone again, obtain the acetone soln of oxygen boryl compound.Then add 0.03gTEMPO and 7g yellow soda ash again, drip acetone soln and the stirring that 100ml contains 6.0g TCCA down, react 60min after dropwising again, stopped reaction at 25 ℃.Promptly make target product, productive rate 97%.
Embodiment 12
Difference from Example 1 is, the preparation of 8-bromine n-octaldehyde: 8-bromine n-caprylic acid 13.3g (60mmol) is dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the tetrahydrofuran solution, add the 50ml methylene dichloride again, obtain the dichloromethane solution of oxygen boryl compound.Then add 0.01g TEMPO and 7g yellow soda ash again, drip acetone soln and the stirring that 100ml contains 6.0g TCCA down, react 60min after dropwising again, stopped reaction at 0 ℃.Promptly make target product, productive rate 95%.
Embodiment 13
Difference from Example 1 is, the preparation of Shi Baquan: n-octadecanoic acid 17.0g (60mmol) is dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the anhydrous ether solution, add 50ml acetone again, obtain the acetone soln of oxygen boryl compound.Then add 0.03g TEMPO and 7g yellow soda ash again, drip acetone soln and the stirring that 100ml contains 6.0g TCCA down, react 60min after dropwising again, stopped reaction at 10 ℃.Promptly make target product, productive rate 94%.
Embodiment 14
Difference from Example 1 is, the preparation of oil aldehyde: oleic acid 16.9g (60mmol) is dissolved in normal temperature dropping 6.6ml (65mmol) borine-dimethyl thioether in the tetrahydrofuran solution, add the 50ml methylene dichloride again, obtain the dichloromethane solution of oxygen boryl compound.Then add 0.01g TEMPO and 7g yellow soda ash again, drip acetone soln and the stirring that 100ml contains 6.0g TCCA down, react 60min after dropwising again, stopped reaction at 40 ℃.Promptly make target product, productive rate 93%.
Claims (6)
1. preparation method who organic carboxyl acid is converted into organic aldehyde, it is characterized in that: in same reactor through two-step reaction, earlier the carboxyl in the carboxylic acid being converted into the oxygen boryl is about to carboxylic acid and is converted into oxygen boryl compound, add quality then and be reaction substrate carboxylic acid quality 0.1%-1.0% 2,2,6,6-tetramethyl piperidine oxide compound and the normal 1.0-1.2 of reaction substrate carboxylic acid alkali doubly, the acetone soln with the normal 1.0-1.2 of reaction substrate carboxylic acid TCCA (Trichloroisocyanuric acid) doubly under 0-40 ℃ is oxidized to aldehyde; Described carboxylic acid is lipid acid and substituted fatty acid or aromatic acid and substituted aroma acid thereof; Described lipid acid and substituted fatty acid are shown below:
R
1For-CH
3, Cl, Br, CO
2CH
3, CO
2C
2H
5N=3-10;
Described aromatic acid and substituted aroma acid thereof are shown below:
R
2＝H、F、Cl、Br、NO
2、CN、COCH
3、CO
2CH
3、CO
2CH
2CH
3。
2. by the described preparation method who organic carboxyl acid is converted into organic aldehyde of claim 1, it is characterized in that: described carboxyl in the carboxylic acid is converted into the oxygen boryl for being dissolved in the 60mmol carboxylic acid in anhydrous diethyl ether or the tetrahydrofuran (THF) and following stirring, normal temperature drips 60-66mmol borine-dimethyl thioether down, dropwising the back refluxes, after removing anhydrous diethyl ether or tetrahydrofuran (THF), the methylene dichloride or the acetone that add 150-200ml again obtain the methylene dichloride or the acetone soln of oxygen boryl compound, and is stand-by.
3. by claim 2 is described organic carboxyl acid is converted into the preparation method of organic aldehyde, it is characterized in that: described backflow 1-2 hour.
4. by claim 1 is described organic carboxyl acid is converted into the preparation method of organic aldehyde, it is characterized in that: the acetone soln of described TCCA (Trichloroisocyanuric acid) is added drop-wise in the reaction solution and stirs; Reacted stopped reaction after dropwising again 1-2 hour.
5. by claim 1 is described organic carboxyl acid is converted into the preparation method of organic aldehyde, it is characterized in that: reaction adds saturated NH with product after finishing
4The Cl aqueous solution is used dichloromethane extraction, and drying is removed and desolvated, and makes to obtain product purification.
6. by claim 1 is described organic carboxyl acid is converted into the preparation method of organic aldehyde, it is characterized in that: described alkali is yellow soda ash, sodium bicarbonate, pyridine, picoline or triethylamine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1746150A (en) * | 2005-08-31 | 2006-03-15 | 四川大学 | Preparation of benzoyl oxy-aldehyde |
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